Silicon compound and a production process for silicon compound

ABSTRACT

The object of the present invention is to provide a new kind of silicon compound having an ester-type organic functional group and a new method for providing a T 8 -silsesquioxane compound having a hydroxyl group by using said silicon compound as the starting material. 
     A silicon compound represented by formula (1) is obtained through the production process characterized by using a silicon compound represented by formula (2). 
                         
wherein:
         in formula (1), each of seven R 1  group is independently selected from the group consisting of hydrogen, alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted arylalkyl and A 2  is a hydroxyl-terminal organic functional group, and in formula (2), each of R 1  group is the same as R 1  in formula (1), and A 1  is an organic functional group containing an acyloxy group.

This application is a Divisional application of Ser. No. 10/664,151,filed Sep. 17, 2003, now U.S. Pat. No. 7,129,370.

FIELD OF THE INVENTION

The present invention relates to a novel synthetic process for a siliconcompound having a hydroxyl group and having a well-defined structure.More specifically, it relates to a production process for asilsesquioxane compound having a hydroxyl group that is useful inapplications including thermoplastic resin modifiers, layer insulators,encapsulants, coating materials and fire retardants by using a new typeof silsesquioxane compound having an organic ester functional group asthe starting material.

BACKGROUND OF THE INVENTION

A known method for introducing hydroxyl groups into a cagesilsesquioxane compound composed of eight silicon atoms (referred to as“T8-silsesquioxane compounds”, hereinafter) comprises of the followingsteps: synthesis of the triflate-group containing silsesquioxane by theaddition of trifluoromethanesulfonic acid to T₈-silsesquioxanecontaining eight intramolecular vinyl groups; and hydrolysis of saidsilsesquioxane in either acetone or dioxane in the presence of sodiumcarbonate (see, e.g., Patent Literature 1 and Nonpatent Literature 1).

However, approximately 85 to 90 percent of the resulting productprepared using the above-described method consists oftrifluoromethansulfonic acid bound to only one vinyl group of eachT₈-silsesquioxane molecule, leaving a proportion of T₈-silsesquioxanecompounds unreacted. Therefore, the target compound must be isolated andpurified from the mixture using techniques such as chromatography,resulting in a complicated process. In addition, the yield of the targetcompound tends to be low.

Patent Literature 1: U.S. Pat. No. 6,100,417.

Nonpatent Literature 1: Chemical Communications, 1289-(1999).

SUMMARY OF THE INVENTION

The object of the present invention is, therefore, to provide abrand-new silicon compound having an ester-type organic functional groupand a novel production process for forming T₈-silsesquioxane compoundhaving a hydroxyl group by using said silicon compound as the startingmaterial.

The above-mentioned problems can be solved by the present invention withthe composition as follows:

-   {1} A production process for a silicon compound represented by    formula (1), characterized by using a silicon compound represented    by formula (2), wherein:

-   -   in formula (1), each of seven R¹ is a functional group        independently selected from the group consisting of (a)        hydrogen, (b) alkyl wherein each hydrogen may be optionally        substituted with fluorine and each —CH₂— group may be optionally        replaced with —O—, —CH═CH—, cycloalkylene or        cycloalkenylene, (c) substituted or unsubstituted aryl, and (d)        substituted or unsubstituted arylalkyl wherein each hydrogen of        the alkylene group may be optionally substituted with fluorine        and each —CH₂— group of said alkylene may be optionally replaced        with ( or —CH═CH—; and A² is a hydroxyl-terminal organic        functional group, and in formula (2), each of R¹ is the same as        R¹ in formula (1), and A¹ is an organic functional group        containing an acyloxy group.

-   {2} The production process as described in the item {1}, wherein    each of seven R¹ in formula (1) is independently selected from the    group consisting of: hydrogen; C₁-C₄₅ alkyl wherein each hydrogen    may be optionally substituted with fluorine and each —CH₂— group may    be optionally replaced with —O—, —CH═CH—, cycloalkylene, or    cycloalkenylene; substituted or unsubstituted aryl; and substituted    or unsubstituted arylalkyl wherein each hydrogen of the alkylene is    optionally substituted with fluorine and each —CH₂— group of said    alkylene may be optionally replaced with —O— or —CH═CH—.

-   {3} The production process as described in the item {1}, wherein    each of seven R¹ in formula (1) is independently selected from the    group consisting of: hydrogen; and C₁-C₃₀ alkyl wherein each    hydrogen may be optionally substituted with fluorine, and each —CH₂—    group may be optionally replaced with -—O— or cycloalkylene.

-   {4} The production process as described in the item {1}, wherein    each of seven R¹ in formula (1) is independently selected from the    group consisting of: C₁-C₂₀ alkenyl wherein each hydrogen may be    optionally substituted with fluorine and each —CH₂— group may be    optionally replaced with —O— or cycloalkylene; and C₁-C₂₀ alkyl    wherein each —CH₂— group is optionally replaced with cycloalkenylene    and in the —CH₂— group optionally replaced with cycloalkylene, each    hydrogen may be optionally substituted with fluorine.

-   {5} The production process as described in the item {1}, wherein    each of seven R¹ in formula (1) is independently selected from the    group consisting of: naphthyl; and phenyl wherein each hydrogen may    be optionally substituted with halogen or C₁-C₁₀ alkyl where each    hydrogen maybe optionally substituted with fluorine and each —CH₂—    group may be optionally replaced with —O—, —CH═CH—, cycloalkylene or    phenylene.

-   {6} The production process as described in the item {1}, wherein    each of seven R¹ in formula (1) is independently selected from the    group consisting of phenylalkyls: wherein each hydrogen atom in a    benzene ring may be optionally substituted with halogen or C₁-C₁₂    alkyl where each hydrogen may be optionally substituted with    fluorine and each —CH₂— group may be optionally replaced with -—O—,    —CH═CH—, cycloalkylene or phenylene, and in the alkylene of the    phenylalkyl, the number of carbons of the alkylene group is 1 to 12;    each hydrogen of said alkylene group may be optionally    substituted-with fluorine; and each —CH₂— group of said alkylene    group may be optionally replaced with —O— or —CH═CH—.

-   {7} The production process as described in the item {1}, wherein    each of seven R¹ in formula (1) is independently selected from the    group consisting of; C₁-C₈ alkyl wherein each hydrogen may be    optionally substituted with fluorine and each —CH₂— group may be    optionally replaced with —O—, —CH═CH—, cycloalkylene or    cycloalkenylene; phenyl wherein each hydrogen may be optionally    substituted with halogen, methyl or methoxy; unsubstituted naphthyl;    and phenylalkyl wherein (a) each phenyl hydrogen may be optionally    substituted with fluorine, C₁-C₄ alkyl, ethenyl or methoxy, (b) the    number of carbons of the alkylene is 1 to 8, and each —CH₂— group of    said alkylene may be optionally replaced with —O— or —CH═CH—.

-   {8} The production process as described in the item {1}, wherein all    of seven R¹ in formula (1) are the same functional groups selected    from the group consisting of: C₁-C₈ alkyl wherein each hydrogen may    be optionally substituted with fluorine and each —CH₂— group may be    optionally replaced with —O—, —CH═CH—, cycloalkylene or    cycloalkenylene; phenyl wherein each hydrogen may be optionally    substituted with halogen, methyl or methoxy; unsubstituted naphthyl;    and phenylalkyl wherein (a) each phenyl hydrogen may be optionally    substituted with fluorine, C₁-C₄ alkyl, ethenyl or methoxy, (b) the    number of carbons of the alkylene is 1 to 8, and each —CH₂— group of    said alkylene may be optionally replaced with —O— or —CH═CH—.

-   {9} The production process as described in the item {1}, wherein all    of seven R¹ in formula (1) are the same functional groups selected    from C₁-C₈ alkyls wherein each hydrogen may be optionally    substituted with fluorine and each —CH₂— group may be optionally    replaced with —O—, —CH═CH—, cycloalkylene, or cycloalkenylene.

-   {10} The production process as described in the item {1}, wherein    all of seven R¹ in formula (1) are the same functional groups    selected from the group consisting of: phenyl wherein each hydrogen    may be optionally substituted with halogen, methyl or methoxy;    naphthyl; and phenylalkyl wherein (a) each hydrogen of the phenyl    may be substituted with fluorine, C₁-C₄ alkyl, ethenyl or    methoxy, (b) the number of carbons of the alkylene group is 1 to 8,    and each —CH₂— group of said alkylene may be optionally replaced    with —O—.

-   {11} The production process as described in the item {1}, wherein A²    in formula (1) is a group represented by formula (3), and A¹ in    formula (2) is a group represented by formula (4),

-    wherein:    -   in formula (3), Z¹ is (a) C₁-C₂₂ alkylene where each —CH₂— may        be optionally replaced with —O—, or (b) C₃-C₈ alkenylene where        each —CH₂— may be optionally replaced with —O—; and in formula        (4), R² is selected from the group of C₁-C₁₇ alkyl where each        hydrogen may be optionally substituted with fluorine, C₂-C₃        alkenyl, substituted or unsubstituted phenyl and unsubstituted        phenylalkyl. {12} The production process as described in the        item {1}, wherein A² in formula (1) is a group represented by        formula (5), and A¹ in formula (2) is a group represented by        formula (6),

-    wherein:    -   in formula (5), (a) Z² represents a single bond or C₁-C₃        alkylene and may be bound to the benzene ring at any        position, (b) Z³ is (i) C₁-C₂₂ alkylene where each —CH₂— may be        optionally replaced with —O— or (ii) C₃-C₈ alkenylene where each        —CH₂— may be optionally replaced with —O—, and in formula (6),        R² is selected from the group consisting of C₁-C₁₇ alkyl, C₂-C₃        alkenyl, substituted or unsubstituted phenyl and unsubstituted        phenylalkyl, and Z² and Z³ are the same as Z² and Z³ in formula        (5).-   {13} The production process as described in the item {11}, wherein:    Z¹ in formula (3) is C₁-C₂₂ alkylene where each —CH₂— group may be    optionally replaced with —O—; and R² in formula (4) is selected from    the group consisting of C₁-C₁₇ alkyl where each hydrogen may be    optionally substituted with fluorine, and C₂-C₃ alkenyl where each    —CH₂— group may be optionally replaced with —O—. {14} The production    process as described in the item {11}, wherein Z¹ in formula (3) is    C₁-C₆ straight-chain alkylene where each —CH₂— group may be    optionally replaced with —O—; and R² in formula (4) is methyl.-   {15} The production process as described in the item {12}, wherein    Z² in formula (5) represents a single bond or C₁-C₃ alkylene where    each —CH₂— group may be optionally replaced with —O—, and Z³ is    C₁-C₂₂ alkylene where each —CH₂— group may be optionally replaced    with —O— and may be bound to the benzene ring at any carbon    position; and R² in formula (6) is selected from the group    consisting of (a) C₁-C₁₇ alkyl where each hydrogen may be optionally    substituted with fluorine and each —CH₂— group may be optionally    replaced with —O—, and (b) C₂-C₃ alkenyl where each —CH₂— group may    be optionally replaced by —O—.-   {16} The production process as described in the item {12}, wherein    Z² in formula (5) represents a single bond or —CH₂—, Z³ in    formula (5) is -C₂H₄₋, and R² in formula (6) is methyl.-   {17} The production process as described in the item {1}, wherein    all of seven R¹ in formula (1) are the same groups selected from the    group consisting of ethyl, 2-methylpropyl, 2,4,4-trimethylpentyl,    cyclopentyl, cyclohexyl, trifluoropropyl,    tridecafluoro-1,1,2,2-tetrahydrooctyl, and unsubstituted phenyl.-   {18} The production process as described in the item {1}, wherein    all of seven R¹ in formula (1) are either unsubstituted phenyl or    trifluoropropyl.-   {19} A silicon compound represented by formula (2),

-    wherein: in formula (2), each of seven R¹ is independently selected    from the group consisting of (a) hydrogen, (b) alkyl where each    hydrogen may be optionally substituted with fluorine and each —CH₂—    group may be optionally replaced with —O—, —CH═CH—, cycloalkylene or    cycloalkenylene, (c) substituted or unsubstituted aryl, and (d)    substituted or unsubstituted arylalkyl where each hydrogen of the    alkylene may be optionally substituted with fluorine and each —CH²—    group of said alkylene may be optionally replaced with (or —CH═CH—;    and A¹ is an organic group that has an acyloxy group.-   {20} The silicon compound as described in the item {19}, wherein A¹    in formula (2) is a group represented by formula (4),

-    wherein: in formula (4), R² is selected from the group consisting    of (a) C₁-C₁₇ alkyl where each hydrogen may be optionally    substituted with fluorine, (b) C₂-C₃ alkenyl, (c) substituted or    unsubstituted phenyl and (d) unsubstituted phenylalkyl; and Z¹ is    either C₁-C₂₂ alkylene where each —CH₂— group may be optionally    replaced with —O—, or C₃-C₈ alkenylene where each —CH₂—group may be    optionally replaced by —O—.-   {21} The silicon compound as described in the item {19}, wherein A¹    in formula (2) is a group represented by formula (6),

-    wherein: in formula (6), R² is selected from the group consisting    of C₁-C₁₇ alkyl; C₂-C₃ alkenyl; substituted or unsubstituted phenyl    and unsubstituted phenylalkyl; and Z² represents a single bond or    C₁-C₃ alkylene that may be bound to the benzene ring at any carbon    position; and Z³ is either C₁-C₂₂ alkylene where each —CH₂— group    may be optionally replaced with —O—, or C₃-C₈ alkenylene where each    —CH₂— may be optionally replaced by —O—.-   {22} The production process as described in the item {1},    characterized by providing a silicon compound represented by    formula (2) through reacting a trichlorosilane compound having an    acyloxy group with either (a) a compound represented by formula (7)    or (b) a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formulas (7) and (12), R¹ is the same as R¹ in    formula (1) and M is a monovalent alkali metal atom.-   {23} The production process as described in the item {11},    characterized by providing a silicon compound represented by    formula (10) through reacting a compound represented by formula (8)    with a compound represented by formula (7) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (7), R¹ is the same as R¹ in formula (1) as    described in the item {1}, in formula (8), R² and Z¹ are the same as    R² and Z¹ in formula (4) as described in the item {11}, and in    formula (10), R¹, R² and Z¹ are the same as R¹, R² and Z¹ in    formulas (7) and (8).-   {24} The production process as described in the item {12},    characterized by providing a silicon compound represented by    formula (11) through reacting a compound represented by formula (9)    with a compound represented by formula (7) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (7), R¹ is the same as R¹ in formula (1) as    described in the item {1}, in formula (9), R², Z², and the binding    position thereof to the benzene ring are the same as R², Z², and the    binding position thereof to the benzene ring in formula (6) as    described in the item {12}, and in formula (11), the characters and    the binding position thereof to the benzene ring are the same as the    characters and the binding position thereof to the benzene ring in    formulas (7) and (9). {25} The production process as described in    the item {11}, characterized by providing a silicon compound    represented by formula (10) through reacting a compound represented    by formula (8) with a compound represented by formula (7) and    acid-catalyzed transesterificating in alcohol,

-    wherein: in formula (7), all of seven R¹ are the same functional    groups selected from the group consisting of ethyl, 2-methylpropyl,    2,4,-trimethylpentyl, cyclopentyl, cyclohexyl, trifluoropropyl,    tridecafluoro-1,1,2,2-tetrahydrooctyl and unsubstituted phenyl, in    formula (8), R² and Z¹ are the same as R² and Z¹ in formula (4) as    described in the item {11}, and in formula (10), R¹,R² and Z¹ are    the same as R¹,R² and Z¹ in formula (7) and (8).-   {26} The production process as described in the item {11},    characterized by providing a silicon compound represented by    formula (10) through reacting a compound represented by formula (8)    with a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (12), R¹ is the same as R¹ in formula (1) as    described in the item {1} and M is a monovalent alkali metal atom,    in formula (8), R² and Z¹ are the same as R² and Z¹ in formula (4)    as described in the item {11}, and in formula (10), R¹, R², and Z¹    are the same as R¹, R², and Z¹ in formulas (12) and (8).-   {27} The production process as described in the item {12},    characterized by providing a silicon compound represented by    formula (11) through reacting a compound represented by formula (9)    with a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (12), R¹ is the same as R¹ in formula (1) as    described in the item {1} and M is a monovalent alkali metal atom,    in formula (9), R², Z², Z³, and the binding position thereof to the    benzene ring are the same as R², Z², Z³, and the binding position    thereof to the benzene ring in formula (6) as described in the item    {12}, and in formula (11), the characters and the binding position    thereof to the benzene ring are the same as the characters and the    binding position thereof to the benzene ring in formulas (12) and    (9).-   {28} The production process as described in the item {11},    characterized by providing a silicon compound represented by    formula (10) through reacting a compound represented by formula (8)    with a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (12), all of seven R¹ are the same groups    selected from the group consisting of (i) C₁-C₈ alkyl where each    hydrogen may be optionally substituted with fluorine and each —CH₂—    group may be optionally replaced with —O—, —CH═CH—, cycloalkylene or    cycloalkenylene, (ii) phenyl where each hydrogen may be optionally    substituted with halogen, methyl or methoxy, (iii) unsubstituted    naphthyl and (iv) phenylalkyl where (A) each benzene hydrogen may be    substituted with fluorine, C₁-C₄ alkyl ethenyl or methoxy, (B) each    —CH₂— group of the alkylene may be optionally replaced with —O— or    —CH═CH—, and M is a monovalent alkali metal atom, in formula (8), R²    and Z¹ are the same as R² and Z¹ in formula (4) as described in the    item {11}, and in formulas (12) and (8).-   {29} The production process as described in the item {11},    characterized by providing a silicon compound represented by    formula (10) through reacting a compound represented by formula (8)    with a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (12), all of seven R¹ are the same groups    selected from the group consisting of (i) ethyl, (ii)    2-methylpropyl, (iii) 2,4,4,-trimethylpentyl, (iv) cyclopentyl, (v)    cyclohexyl, (vi) trifluoropropyl, (vii)    tridecafluoro-1,1,2,2-tetrahydrooctyl, and (viii) unsubstituted    phenyl, and M is a monovalent alkali metal atom, in formula (8), R²    and Z¹ are the same as R² and Z¹ in formula (4) as described in the    item {11} of formula (10), R¹, defined below through reaction of (a)    a compound of formula (12), and in formula (10), R¹, R² and Z¹ are    the same as R¹, R² and Z¹ in formulas (12) and (8).-   {30} The production process as described in the item {12},    characterized by providing a silicon compound represented by    formula (11) through reacting a compound represented by formula (9)    with a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (12), all of seven R¹ are the same groups    selected from the group consisting of (i) C₁-C₈ alkyl wherein each    hydrogen may be optionally substituted with fluorine and each —CH₂—    group may be optionally replaced with —O—, —CH═CH—, cycloalkylene or    cycloalkenylene, (ii) phenyl wherein each hydrogen may be optionally    substituted with halogen, methyl or methoxy, (iii) unsubstituted    naphthyl and (iv) phenylalkyl wherein each benzene hydrogen is    optionally substituted with fluorine, C₁-C₄ alkyl, ethenyl or    methoxy and each —CH₂— group of the alkylene may be optionally    replaced with —O— or —CH═CH—, and M is a monovalent alkali metal    atom, in formula (9), R², Z², Z³, and the binding position thereof    to the benzene ring and are the same as R², Z², Z³, and the binding    position thereof to the benzene ring in formula (6) as described in    the item {12}, and in formula (11), the characters and the binding    position thereof to the benzene ring are the same as the characters    and the binding position thereof to the benzene ring in    formulas (12) and (9).-   {13} The production process as described in the item {12},    characterized by providing a silicon compound represented by    formula (11) through reacting a compound represented by formula (9)    with a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (12), all of seven R¹ are the same groups    selected from the group consisting of (i) ethyl, (ii)    2-methylpropyl, (iii) 2,4,4-trimethylpentyl, (iv) cyclopentyl, (v)    cyclohexyl, (vi) trifluoropropyl, (vii)    tridecafluoro-1,1,2,2-tetrahydrooctyl and (viii) unsubstituted    phenyl, and M is a monovalent alkali metal atom, in formula (9), R²,    Z², Z³, and the binding position thereof to the benzene ring are the    same as R², Z², Z³, and the binding position thereof to the benzene    ring in formula (6) as described in the item {12}, and in formula    (11), the characters and the binding position thereof to the benzene    ring are the same as the characters and the binding position thereof    to the benzene ring in formulas (12) and (9).-   {32} The production process as described in the item {12},    characterized by providing a silicon compound represented by    formula (11) through reacting a compound represented by formula (9)    with a compound represented by formula (12) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (12), all of seven R¹ are either unsubstituted    phenyl or trifluoropropyl and M is a monovalent alkali metal atom,    in formula (9), R², Z², Z³, and the binding position thereof to the    benzene ring are the same as R², Z², Z³, and the binding position    thereof to the benzene ring in formula (6) as described in the item    {12}, and in formula (11), the characters and the binding position    thereof to the benzene ring are the same as the characters and the    binding position thereof to the benzene ring in formulas (12) and    (9).-   {33} A silicon compound represented by formula (1), being prepared    from a silicon compound represented by formula (2),

-    wherein: in formula (1), each of seven R¹ is independently selected    from the group consisting of (a) hydrogen, (b) C₁-C₄₅ alkyl wherein    each hydrogen may be optionally substituted with fluorine and each    —CH₂— group may be optionally replaced with —O—, —CH═CH—,    cycloalkylene or cycloalkenylene, (c) substituted or unsubstituted    aryl and (d) substituted or unsubstituted arylalkyl wherein each    hydrogen of the alkenylene may be optionally substituted with    fluorine and each —CH₂— group of said alkenylene may be optionally    replaced with —O— or —CH═CH—; and A² is a hydroxyl-terminal organic    group, and in formula (2), R¹ is the same as R¹ in formula (1) and    A¹ is an organic compound having an acyloxy group.-   {34} The silicon compound as described in the item {33}, (a) in    formula (1),all of seven R¹ are the same functional groups selected    from the group consisting of (i) ethyl, (ii) 2-methylpropyl, (iii)    2,4,4-methylpentyl, (iv) cyclopentyl, (v) cyclohexyl, (vi)    trifluoropropyl, (vii) tridecafluoro-1,1,2,2,-tetrahydrooctyl    and (viii) unsubstituted phenyl; (b) A² is a group represented by    formula (3) and (c) A¹ in formula (2) is a group represented by    formula (4),

-    wherein: in formula (3), Z¹ is either C₁-C₂ ₂ alkylene where each    —CH₂— group may be optionally replaced with , or C₃-C₈ alkenylene    where each —CH₂— group may be optionally replaced with —O—; in    formula (4), R² is selected from the group consisting of C₁-C₁₇    alkyl where each hydrogen may be optionally substituted with    fluorine, C₂-C₃ alkenyl, substituted or unsubstituted phenyl and    unsubstituted phenylalkyl, and Z¹ is the same as Z¹ in formula (3).-   {35} The silicon compound as described in the item {33}, (a) in    formula (1), all of seven R¹ are the same functional groups selected    from the group consisting of (i) ethyl, (ii) 2-methylpropyl, (iii)    2,4,4trimethylpentyl, (iv) cyclopentyl, (v) cyclohexyl, (vi)    trifluoropropyl, (vii) tridecafluoro-1,1,2,2,-tetrahydrooctyl    and (viii) unsubstituted phenyl; (b) A¹ is a group represented by    formula (5) and (c) A¹ in formula (2) is a group represented by    formula (6),

-    wherein: in formula (5), (A) Z² represents a single bond or C₁-C₃    alkylene and may be bound to the benzene ring at any carbon    position, (B) Z³ is either C₁-C₂₂ alkylene where each —CH₂— may be    optionally replaced with —O—, or C₃-C₈ alkenylene where each —CH₂—    may be optionally replaced with —O—, in formula (6), R² is selected    from the group consisting of C₁-C₁₇ alkyl, C₂-C₃ alkenyl,    substituted or unsubstituted phenyl and unsubstituted phenylalkyl,    and Z² and Z³ are the same as Z¹ and Z³ in formula (5).-   {36} The silicon compound as described in the item {34}, wherein all    of seven R¹ are either unsubstituted phenyl or trifluoropropyl.-   {37} The silicon compound as described in the item {35}, wherein all    of seven R¹ are either unsubstituted phenyl or trifluoropropyl.-   {38} The production process as described in the item {12},    characterized by providing a silicon compound represented by    formula (11) through reacting a compound represented by formula (9)    with a compound represented by formula (7) and acid-catalyzed    transesterificating in alcohol,

-    wherein: in formula (7), all of seven R¹ are the same group    selected from the group consisting of (i) ethyl, (ii)    2-methylpropyl, (iii) 2,4,4-trimethylpentyl, (iv) cyclopentyl, (v)    cyclohexyl, (vi) trifluoropropyl, (vii)    tridecafluoro-1,1,2,2-tetrahydrooctyl and (viii) unsubstituted    phenyl, in formula (9), R², Z², Z³, and the binding position thereof    to the benzene ring are the same as R², Z², Z³, and the binding    position thereof to the benzene ring in formula (6) as described in    the item {12}, and in formula (11), the characters and the binding    position thereof to the benzene ring are the same as the characters    and the binding position thereof to the benzene ring in formulas (7)    and (9).

EFFECTS: The method according to the invention allows the simplifiedproduction of silsequioxane compounds with hydroxyl groups.Silsesquioxane compounds of this type are extremely useful as aprecursor to derive many types of silsesquioxane compounds. Hydroxylgroups of those silsesquioxane compounds can increase solubilities ofT₈-silsesquioxane compounds in organic solvents, and mutual solubilitiesof resins in the preparation of organic-inorganic composite materials.Therefore, T₈-silsesquioxane compounds having hydroxyl groups accordingto the invention are useful not only as precursors to derive many typesof silsesquioxanes, but also as resin modifiers.

DETAILED DESCRIPTION OF THE INVENTION

The terms used in the invention are defined as follows: both “alkyl” and“alkylene” may be straight-chained and branched groups. This applies tothe cases where each hydrogen of said groups is optionally replaced withhalogens or cyclic compounds and where each —CH₂— group of said groupsis optionally replaced with —O—, —CH═CH—, cycloalkylene, cycloalkenyleneor phenylene. If two or more hydrogen atoms or —CH₂— groups have beensubstituted, the substituents can be the same or different from eachother. In an alkyl group, for example, two —CH₂— groups have beenreplaced with —O— and —CH═CH—, the said group represents eitheralcoxyalkenyl or alkenyloxyalkyl. In this case, the groups of alcoxy,alkenylene, alkenyl and alkylene can be straight-chained or branched.However, there must not be consequent —CH₂— groups between substituentsof —O— in alkyl or alkylene groups.

Hereinafter, there are cases in which a compound in formula (1) isrepresented as a compound (1). The same applies to other compounds inother formulas. The production process for a compound (1) according tothe present invention is characterized by using a compound (2).

That is, R¹ in formula (2) is the same as R¹ in formula (1). In formula(1), each of seven R¹ is independently selected from the groupconsisting of hydrogen, alkyl groups, substituted or unsubstituted arylgroups, and substituted or unsubstituted arylalkyl groups. All of sevenR¹ groups are preferably the same, but may be of two or more differentgroups. The latter case includes: two or more alkyl groups; two or morearyl groups; two or more aralkyl groups; a combination of hydrogen andat least one aryl group; a combination of at least one alkyl group andat least one aryl group; a combination of at least one alkyl group andat least one aralkyl group; and a combination of at least one aryl groupand at least one aralkyl group. A compound of formula (1) where R¹comprises of two or more different groups is prepared from two or moredifferent raw materials, which are described thereinafter.

When R¹ is alkyl, the number of carbons is between 1 and 45. It shouldbe preferably between 1 and 30, and more preferably between 1 and 8. Inthe alkyl groups, each hydrogen may be optionally substituted withfluorine and each —CH₂— group may be optionally replaced with —O—,—CH═CH—, cycloalkylene or cycloalkenylene. Preferred examples of alkylgroups include unsubstituted C₁-C₃₀ alkyl C₂-C₂₉ alcoxyalkyl, C₁-C₈alkyl where one —CH₂— group is replaced with cycloalkylene, C₂-C₂₀alkenyl, C₂-C₂₀ alkenyloxyalkyl, C₂-C₂₀ alkyloxyalkenyl, C₁-C₈ alkylwhere one —CH₂— group is replaced with cycloalkylene, and fluorinatedcompounds thereof. The number of carbons for said cycloalkylene andcycloalkenylene should be preferably between 3 and 8.

Examples of unsubstituted C₁-C₃₀ alkyl include methyl, ethyl, propyl1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl,1,1,2-trimethylpropyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl,decyl, undecyl, dodecyl tetradecyl, hexadecyl, octadecyl, eicosyl,docosyl, and triacontyl. Examples of fluorinated C₁-C₃₀ alkyl include3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonadecafluorohexyl,tridecafluoro-1,1,2,2-tetrahydrooctyl,heptadecafluoro-1,1,2,2,-tetrahydrodecyl, perfluoro-1H,1H,2H,2H-dodecyl,and perfluoro-1H,1H,2H,2H-tetradecyl. Examples of C₂-C₂₉ alcoxyalkylinclude 3-methyxypropyl, methoxyethoxyundecyl, and3-heptafluoroisopropoxypropyl. Examples of C₁-C₈ alkyl where one —CH₂—group is replaced with cycloalkylene include cyclohexylmethyl,adamantaneetyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl, andcyclooctyl. Cyclohexyl is an example where one —CH₂— group of methyl isreplaced with cyclohexylene. Cyclohexylmethyl is an example where one—CH₂— group of ethyl is replaced with cyclohexylene.

Examples of C₂-C₂₀ alkenyl include ethenyl 2-propenyl, 3-butenyl,5-hexenyl, 7-octenyl, 10-undecenyl, and 21-dococenyl. Examples of C₂-C₂₀alkenyloxyalkyl include aryloxyundecyl. Examples of C₁-C₈ alkyl whereone —CH₂— group is replaced with cycloalkenylene include2-(3-cyclohexenyl)ethyl, 5-(bicycloheptenyl)ethyl, 2-cyclopentenyl,3-cyclohexenyl, 5-norbornene-2-yl, and 4-cyclooctenyl.

Examples where R¹ in formula (1) is substituted or unsubstituted aryl,are phenyl or unsubstituted naphthyl of which hydrogen may be optionallysubstituted with a halogen or C₁-C₁₀ alkyl. The halogen is preferablyfluorine, chlorine, and bromine. In the C₁-C₁₀ alkyl, each hydrogen maybe optionally substituted with fluorine and each —CH₂— group may beoptionally replaced with —O—, —CH═CH— or phenylene. Therefore, preferredexamples where R¹ in formula (1) is substituted or unsubstituted arylinclude unsubstituted phenyl, unsubstituted naphthyl, alkyl phenyl,alkyloxyphenyl, alkenylphenyl, phenyl substituted with C₁-C₁₀ alkylwhere one —CH₂— group is replaced with phenylene, and halogenatedcompounds thereof.

Examples of halogenated phenyl include pentafluorophenyl,4-chlorophenyl, and 4bromophenyl. Examples of alkylphenyl include4-methylphenyl, 4-ethylphenyl, 4propylphenyl, 4butylphenyl,4-pentylphenyl, 4heptylphenyl, 4-octylphenyl, 4-nonylphenyl,4-decylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl,2,4,6-triethylphenyl, 4-(1-methylethyl)phenyl,4(1,1-dimethylethyl)phenyl, 4-(2-ethylhexyl)phenyl, and2,4,6-tris(1-methylethyl)phenyl. Examples of alkyloxyphenyl include(4-methoxy)phenyl, (4ethoxy)phenyl, (4-propoxy)phenyl, (4-butoxy)phenyl,(4-pentyloxy)phenyl, (4-heptyloxy)phenyl, (4-decyloxy)phenyl,(4-octadecyloxy)phenyl, 4(1-methylethoxy)phenyl,4(2-methylpropoxy)phenyl, and 4-(1,1-dimethylethoxy)phenyl. Examples ofalkenylphenyl include 4-ethenylphenyl, 4(1-methylethenyl)phenyl and4(3-butenyl)phenyl.

Examples of phenyl substituted with C₁-C₁₀ alkyl where —CH₂— group isoptionally replaced with phenylene include 4(2-phenylethenyl)phenyl,4-phenoxyphenyl, 3-(phenylmethyl)phenyl, biphenyl, and terphenyl.4-(2-phenylethenyl)phenyl is an example of ethylphenyl where one —CH₂—group of the ethyl group is replaced with phenylene and the other groupis replaced with —CH═CH—.

Examples of phenyl of which benzene-ring hydrogens partially substitutedwith halogen and the others substituted with alkyl, alkyloxy or alkenylinclude 3-chloro-4-methylphenyl, 2,5-dichloro-4-methylphenyl,3,5-dichloro-4-methylphenyl, 2,3,5-trichloro-4-methylphenyl,2,3,6-trichloro-4-methylphenyl, 3-bromo-4-methylphenyl,2,5-dibromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl,2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl,3-bromo-4-methoxyphenyl, 3,5-dibromo-4 methoxyphenyl,2,3-difluolo-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl, and2,3-difluoro4-propoxyphenyl, 4-ethenyl-2,3,5,6-tetrafluorophenyl.

If R¹ in formula (1) is a substituted or unsubstituted arylalkyl, eachhydrogen of the alkylene group may be optionally substituted withfluorine and each —CH₂— group may be optionally replaced with —O— or—CH═CH—. A preferred example of arylalkyl is phenylalkyl where thenumber of carbons should be preferably between 1 and 12, and morepreferably between 1 and 8. Examples of phenylalkyl includephenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl,5-phenylpentyl, 6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl,2-phenylpropyl, 1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl,1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl, and1-phenylhexyl.

Each benzene-ring hydrogen of phenylalkyl may be optionally substitutedwith a halogen or C₁-C₁₂ alkyl where each hydrogen may be optionallysubstituted with fluorine and each —CH₂— group may be optionallyreplaced with —O—, —CH═CH—, cycloalkylene or phenylene. Examples ofphenylalkyl substituted on the phenyl ring with fluorine include4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl,2-(2,3,4,5,6-pentafluorophenyl)ethyl,3-(2,3,4,5,6-pentafluorophenyl)propyl, 2-(2-fluorophenyl)propyl and2-(4-fluorophenyl)propyl.

Examples of phenylalkyl of which benzene-ring hydrogen is optionallysubstituted with chlorine include 4-chlorophenylmethyl,2-chlorophenylmethyl, 2,6-dichlorophenylmethyl,2,4-dichlorophenylmethyl, 2,3,6-trichlorophenylmethyl,2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl,2,3,4,6-tetrachlorophenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl,2-(2-chlorophenyl)ethyl, 2-(4-chlorophenyl)ethyl,2-(2,4,5-chlorophenyl)ethyl, 2-(2,3,6-chlorophenyl)ethyl,3-(3-chlorophenyl)propyl, 3-(4-chlorophenyl)propyl,3-(2,4,5-trichlorophenyl)propyl, 3-(2,3,6-trichlorophenyl)propyl,4-(2-chlorophenyl)butyl, 4-(3-chlorophenyl)butyl,4-(4-chlorophenyl)butyl, 4-(2,3,6-trichlorophenyl)butyl,4-(2-4,5-trichlorophenyl)butyl, 1-(3-chlorophenyl)ethyl,1-(4-chlorophenyl)ethyl, 2-(4-chlorophenyl)propyl,2-(2-chlorophenyl)propyl, and 1-(4-chlorophenyl)butyl.

Examples of phenylalkyl of which benzene-ring hydrogen is optionallysubstituted with bromine include 2-bromophenylmethyl,4-bromophenylmethyl, 2,4-dibromophenylmethyl,2,4,6-tribromophenylmethyl, 2,3,4,5-tetrabromophenylmethyl,2,3,4,5,6-pentabromophenylmethyl, 2-(4-bromophenyl)ethyl,3-(4-bromophenylpropyl, 3-(3-bromophenyl)propyl, 4-(4-bromophenyl)butyl,1-(4-bromophenyl)ethyl, 2-(2-bromophenyl)propyl, and2-(4-bromophenyl)propyl.

Examples of phenylalkyl of which benzene-ring hydrogen is optionallysubstituted with C₁-C₁₂ alkyl include 2-methylphenylmethyl,3-methylphenylmethyl, 4-methylphelylmethyl, 4-dodecylphenylmethyl,3,5-methylphenylmethyl, 2-(4-methylphenyl)ethyl,2-(3-methylphenyl)ethyl, 2-(2,5-dimethylphenyl)ethyl,2-(4-ethylphenyl)ethyl, 2-(3-ethylphenyl)ethyl, 1-(4-methylphenyl)ethyl,1-(3-methylphenyl)ethyl, 1-(2-methylphenyl)ethyl,2-(4-methylphenyl)propyl, 2-(2-methylphenyl)propyl,2-(4-ethylphenyl)propyl, 2-(2-ethylphenyl)propyl,2-(2,3-dimethylphenyl)propyl, 2-(2,5-dimethylphenyl)propyl,2-(3,5dimethylphenyl)propyl, 2-(2,4-dimethylphenyl)propyl,2-(3,4-dimethylphenyl)propyl, 2-(2,5-dimethylphenyl)butyl(4-(1-methylethyl)phenyl)methyl, 2-(4-(1,1-dimethylethyl)phenyl)ethyl,2-(4-(1-methylethyl)phenyl)propyl, and2-(3-(1-methylethyl)phenyl)propyl.

Examples of phenylalkyl of which benzene-ring hydrogen is optionallysubstituted with fluorinated C₁-C₁₂ alkyl include3-(trifluoromethyl)phenylmethyl, 2-(4-trifluoromethylphenyl)ethyl,2-(4-nonafluorobutylphenyl)ethyl, 2-(4-tridecafluorohexylphenyl)ethyl,2-(4-heptadecafluorooctylphenyl)ethyl, 1-(3-trifluoromethylphenyl)ethyl,1-(4-trifluoromethylphenyl)ethyl, 1-(4-nonafluorobutylphenyl)ethyl,1-(4-tridecafluorohexylphenyl)ethyl,1-(4-heptadecafluorooctylphenyl)ethyl,2-(4-nonafluorobutylphenyl)propyl,1-methyl-1-(4-nonafluorobutylphenyl)ethyl,2-(4-tridecafluorohexylphenyl)propyl1-methyl-1-(4-tridecafluorohexylphenyl)ethyl,2-(4heptadecafluorooctylphenyl)propyl, and1-methyl-1-(4-heptadecafluorooctylphenyl)ethyl.

Examples of phenylalkyl of which benzene-ring hydrogen is optionallysubstituted with C₁-C₁₂ alkyl where one —CH₂— group is replaced with—CH═CH— include 2-(4-ethenylphenyl)ethyl, 1-(4ethenylphenyl)ethyl, and1-(2-(2-propenyl)phenyl)ethyl. Examples of phenylalkyl substituted onthe phenyl ring by C₁-C₁₂ alkyl where one —CH₂— group is replaced by —O—include 4-methoxyphenylmethyl, 3-methoxyphenylmethyl,4-ethoxyphenylmethyl, 2-(4-methoxyphenyl)ethyl,3-(4-methoxyphenyl)propyl, 3-(2-methoxyphenyl)propyl,3-(3,4-dimethoxyphenyl)propyl, 11-(4-methoxyphenyl)undecyl,1-(4-methoxyphenyl)ethyl, 2-(3-(methoxymethyl)phenyl)ethyl and3-(2-nonadecafluorodecenyloxyphenyl)propyl.

Examples of phenylalkyl of which benzene-ring hydrogen is optionallysubstituted with C₁-C₁₂ alkyl where one —CH₂— group is replaced withcycloalkylene and another —CH₂— group is optionally replaced with —O—include cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl,cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyland cyclohexyloxyphenylmethyl. Examples of phenylalkyl of whichbenzene-ring hydrogen is optionally substituted with C₁-C₁₂ alkyl whereone —CH₂— group is replaced with phenylene another —CH₂— group isoptionally replaced with —O— include 2-(4-phenoxyphenyl)ethyl,2-(4-phenoxyphenyl)propyl, 2-(2-phenoxyphenyl)propyl,4-biphenylylmethyl, 3-biphenylylethyl, 4-biphenylylethyl,4-biphenylylpropyl, 2-(2-biphenylyl)propyl, and 2-(4-biphenylyl)propyl.

Examples of phenylalkyl where at least two of benzene-ring hydrogens aresubstituted with two different groups include3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propyl,3-chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl,5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl,2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmehtyl,2,3-dichloro-4-methylphenylmethyl, 2,5-dichloro-4-methylphenylmethyl,3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl,2,3,5,6-tetrachloro-4-methylphenylmethyl,(2,3,4,6-tetrachloro-5-methylphenyl)methyl,2,3,4,5-tetrachloro-6-methylphenylmethyl,4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl,2,4-dichloro-3,5-dimethylphenylmethyl,2,6-dichloro-3,5-dimethylphenylmethyl,2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl,4-bromo-2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl,6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl,2,3-dibromo-4-methylphenylmethyl, 2,3,5-tribromo-4-methylphenylmethyl,2,3,5,6-tetrabromo-4-methylphenylmethyl, and11-(3-chloro-4-methoxyphenyl)undecyl.

The most preferable phenyls in phenylalkyl are unsubstituted phenyl andphenyl with at least one of the following substutuents: fluorine; C₁-C₄alkyl; ethenyl; and methoxy.

Examples of phenylalkyl where one —CH₂— group of the alkylene isreplaced with —O— or —CH═CH— include 3-phenoxypropyl, 1-phenylethenyl,2-phenylethenyl, 3-phenyl-2-propenyl, 4-phenylpentenyl, and13-phenyl-12-tridecenyl. Examples of phenylalkyl substituted on thephenyl ring by fluorine or methyl include 4-fluorophenylethenyl,2,3-difluorophenylethenyl, 2,3,4,5,6-pentafluorophenylethenyl, and4-methylphenylethenyl.

The most preferable examples of R¹ are C₂-C₈-alkyl(say, ethyl isobutyland isooctyl)-phenyl halogenated phenyl, phenyl substituted with atleast one methyl group, methoxyphenyl naphthyl, phenylmethyl,phenylethyl, phenylbutyl, 2-phenylpropyl, 1-methyl-2-phenylethyl,pentafluorophenylpropyl, 4-ethylpheylethyl, 3-ethylphenylethyl,4-(1,1-dimethylethyl)phenylethyl, 4-ethenylphenylethyl,1-(4-ethenylphenyl)ethyl, 4-methoxyphenylpropyl, and phenoxypropyl.

A² is preferably a hydroxyl-terminal organic groups represented byformula (3) or (5).

Then, the functional group represented by formula (3) is explainedparticularly.H—O-Z¹-  (3)Referring to Z¹ in formula (3), preferable examples is C₁-C₂₂ alkyleneor C₃-C₈ alkenylene, and its specific example is a group in formulas(13) to (29). More preferably, Z¹ is C₁-C₂₂ alkylene, and its specificexample is a group in formulas (13) to (25). The most preferable exampleof Z¹ is C₁-C₆ straight-chained alkylene, and its specific example is agroup in formula (13), (14), (15), (22) and (23). In the alkylenealkenylene groups, each —CH₂— group may be optionally replaced with —O—.

Then, the functional group represented by formula (5) is explainedparticularly.

Referring to the group in formula (5), preferably, Z² is a single bondor C₁-C₃ alkylene, and Z³ is C₁-C₂₂ alkylene or C₃-C₈ alkenylene, andtheir specific examples are groups in formulas (30) to (37). Morepreferably, Z² is a single bond or C₁-C₃ alkylene, and Z³ is C₁-C₂₂alkylene. In the most preferred example, Z² is a single bond or —CH₂—,and Z³ is C₂H₄, and their specific examples are groups in formulas (30)and (34). Each —CH₂— of the alkylene or alkenylene groups may beoptionally replaced with —O—, and Z² can be bound to the benzene ring atany carbon position.

Then, the production process for the silicon compound of the presentinvention is explained. One of a preferable raw material of the presentinvention is a silicon compound represented by formula (2),

-   -   Wherein: in formula (2), R¹ is the same as R¹ in formula (1),        and A¹ is preferably an organic group that has an acyloxy group        represented by formula (4) or (6).

Then, the functional group represented by formula (4) is explainedparticularly.

-   -   Referring to formula (4), preferably, R² is selected from the        group consisting of C₁-C₁₇ alkyl, C₂-C₃ alkenyl, substituted or        unsubstituted phenyl, and unsubstituted phenylalkyl and Z¹ is        C₁-C₂₂ alkylene or C₃-C₈ alkenylene, and their specific examples        are groups in formulas (38) to (78). More preferably, Z¹ is        C₁-C₂₂ alkylene, and R² is either C₁-C₁₇ allyl or C₂-C₃ alkenyl,        and their specific examples are groups in formulas (38) to        (55), (61) to (64) and (69) to (78). Most preferably, Z¹ is        straight-chained C₁-C₆ alkylene, and R² is a methyl group, and        their specific examples are groups in formulas (33), (34), (38)        or (39). Each hydrogen of the alkyl groups is optionally        substituted with fluorine. Each —CH₂— group of the alkylene or        alkenylene groups may be optionally replaced with —O—.

Then, the functional group represented by formula (6) is explainedparticularly.

-   -   Referring to formula (6), preferably, R² is selected from the        group consisting of C₁-C₁₇ alkyl, C₂-C₃ alkenyl, substituted or        unsubstituted phenyl, unsubstituted phenylalkyl, Z² is either a        single bond or C₁-C₃ alkylene, and Z³ is either C₁-C₂₂ alkylene        or C₃-C₈ alkenylene, and their specific examples are        formulas (79) to (102). More preferably, R² is either C₁-C₁₇        alkyl or C₂-C₃ alkenyl, Z² is either a single bond or C₁-C₃        alkylene, and Z³ is C₁-C₂₂ alkylene. Most preferably, R² is        methyl, Z² is either a single bond or —CH₂—, and Z³ is —C₂H₄—,        and their specific examples are formulas (79) and (83). Each        —CH₂— group of the alkylene and alkenylene groups may be        optionally replaced with —O—. Z² can be bound to the benzene        ring at any carbon position.

Then, the production process for the present invention is explained. Apreferable raw material of a silicon compound represented by formula (2)is a silicon compound (silsesquioxane compound) that has a silanol grouprepresented by formula (7).

R¹ in formula (7) is the same as R¹ in formula (2). Such a compound canbe prepared through hydrolysis and maturation of chlorosilane. Forexample, Frank J. Feher et al have prepared a compound in formula (7)with R¹ being cyclopentyl by reacting cyclopentyltrichlorosilane inwater-acetone mixed solvent at room temperature or reflux temperature,and maturing for two weeks (Organometallics, 10, 2526-(1991), andChemical European Journal, 3, No. 6, 900-(1997)). A compound (2) can beprepared by reacting a compound (7) with trichlorosilane having anacyloxy group by utilizing the reactivity of silanol (Si—OH). Preferabletrichlorosilane which has an acyloxy group is a compound (8) or (9).

A compound (10) can be prepared by reacting a compound (7) with acompound (8).

In consideration of using a commercially available compound (7), apreferable example of R¹ in formula (7) is selected from a groupconsisting of: C₁-C₈ alkyl wherein each hydrogen may be optionallysubstituted with fluorine and each —CH₂— group may be optionallyreplaced with —O—, —CH═CH—, cycloalkylene or cycloalkenylene; phenylwherein each hydrogen may be optionally substituted with halogen, methylor methoxy; unsubstituted naphthyl; and phenylalkyl wherein eachhydrogen atom in a benzene ring may be optionally substituted withfluorine, C₁-C₄ alkyl, ethenyl or methoxy and each —CH₂— group may beoptionally replaced with —O—, and other characters in formulas (8) and(10) are the same as defined above.

A compound ( 1) can be obtained by reacting a compound (7) with acompound (9).

Preferable examples of R¹ in formula (7) are the same as defined above.The other symbols of formula (9) and (11) are as defined above. Thebinding position of Z² is as defined above.

A compound (2) can be prepared from compounds (7) and (8) or compounds(7) and (9) through the “Comer-capping reaction,” a reaction utilizingwhat is called nucleophilic substitution as described in, for example,Macromolecules, 28, 8435-(1995).

The selection conditions for solvents used in the above-describednucleophilic substitution reaction are as follows: they do not reactwith compounds (7) and (8) or compounds (7) and (9); and they aresufficiently dehydrated Examples of these solvents includetetrahydrofuran, toluene, and dimethylformamide and so on, and the mostpreferable solvent is sufficiently dehydrated tetrahydrofuran. Inconsideration of full reaction of Si—OH (silanol) group of the compound(7), the preferable equivalent ratio of the compound (8) or (9) to theSi—OH (silanol) group of the compound (7) is 1 to 5. Becausehydrochloride is generated through the reaction of the hydrogen ofsilanol and the chlorine of the chlorosilan, it must be removed from thereaction system. Although there is no limitation on the removing methodof hydrochloride, ; various organic bases are preferably used. Though,any bases may be used as long as they allow the inhibition of sidereactions and the smooth progress of the main reaction, for example,pyridine, dimethylaniline, triethylamine, triethylamine, andtetramethylurea are indicated, and most preferable organic base istriethylamine. The equivalent ratio of triethylamine to the Si—OH groupof a compound (7) is preferably 3 to 5. Reaction temperature is that atwhich quantitative nucleophilic substitution reactions occur withoutside reactions. Raw materials can be prepared at low temperature, andmost preferably, say, in an ice bath. The downstream procedures can beoperated at room temperature. No particular restriction is imposed onthe reaction time; any time may be used as long as enough quantitativenucleophilic reactions proceed. Usually, the silicon compound (2) isobtained for a reaction time of 13 hours.

Another preferable raw material employed in the invention is asilsesquioxane compound represented by formula (12).

-   -   The compound (12) can be prepared by the steps of: hydrolysis of        a silane compound having trifunctional hydrolyzable groups to        obtain a silsesquioxane oligomer, and reaction of the oligomer        with a monovalent alkali-metal hydroxide in an organic solvent        The compound (12) can also be prepared through hydrolysis and        condensation of a silane compound having trifunctional        hydrolysable groups in the presence of water and a monovalent        alkali-metal hydroxide. Using both methods, the compound (12)        can be prepared for a shot with a high yield (see, for example,        Pat. No. PCT/JP02/04776). Because the compound (12) has a higher        reactivity than the silanol groups of compound (7), its        derivatives can easily be prepared from it with a high yield. In        addition, the compound (12) has —ONa groups as its reactive        groups, so reaction procedures are easy and reaction can be        finished completely. That is, a compound (1) can easily be        prepared from a compound (12) and trichlorosilane having an        acyloxy group.

It is also preferable, that a compound (10) is prepared by reacting saidcompound (8), in case of utilizing a compound (12). R¹ in formula (12)is the same as R¹ in formula (1), and its preferable examples are asdescribed for formula (7). M in formula (12) is a monovalent alkalimetal atom, preferably sodium or potassium, and most preferably sodium.A compound (10) can be prepared by reacting a compound (12) with acompound (8) according to the method using a compound (7). Theequivalent ratio of the compound (8) to the Si-ONa group of the compound(12) should preferably range from 1 to 5. Although this reactionrequires no organic bases to remove hydrochloride, they may be used ascatalysts to permit a smooth reaction progress. Organic bases that allowthe inhibition of side reactions and smooth progress of the mainreaction include, though not restricted specifically, for example,pyridine, dimethylaniline, triethylamine, and tetramethylurea, and morepreferably, triethylamine. The equivalent ratio of triethylamine to theSi—ONa group of the compound (12) should preferably range from 3 to 5.Solvents, reaction temperature and reaction times are as defined for thereaction using a compound (7). A compound (11) can be prepared byreacting the compound (12) with said compound (9) according to themethod for preparing a compound (10) from a compound (8).

If a distillation method is used to remove unreacted raw materials orsolvents (both of which may be referred to as impurities hereinafter),the main resulting product is maintained at a high temperature for aprolonged period of time, which may lead to decomposition. Preferably,purification through recrystallization or the extraction of impuritieswith organic solvents would be used to efficiently remove impuritieswithout a significant reduction in purity of the compounds (10) and(11). Using the compound (10) as an example, the purification methodthrough recrystallization is explained particularly. This purificationis performed as follows: first, the impurities containing substance isfirst dissolved in a solvent, with a preferable concentration of 1 to 15percent by weight. The solution is transferred into concentrationequipment, such as a rotary evaporator, and concentrated under reducedpressure until precipitation of a crystal has been initiated. Themixture is then maintained at atmospheric pressure and room or lowtemperature, and filtrated through a filter or centrifugally separatedto separate the crystallized solid and the solvent containingimpurities. The solvent also includes some of the crystal, and theabove-described procedures may be repeated to increase the yield of thecompound (10). The same applies to the process for removing impuritiesin the compound (11).

The selection condition of preferable solvents used forrecrystallization is; it does not react with the compound (10), itdissolves the compound and impurities completely before condensation, itdissolves only the impurities and crystallize the compound with highefficiency during condensation, and it has relatively low boiling point,and so on. Examples of preferable solvents meeting these conditions areesters and aromatics, and the most preferably solvents are ethyl acetateand toluene. In addition, a higher purity can be achieved through largerepeat number of the recrystallization procedure. The same conditionsfor selecting solvents apply to recrystallization of the compound (11).

Using the compound (10) as an example, the method for extractingimpurities with an organic solvent is explained particularly. Thisextraction method is performed as follows: first, the compound (10)containing impurities is transferred into an organic solvent thatdissolves only the impurities. The mixture is stirred to extract onlythe impurities, and the remaining solid is isolated through filtrationor centrifugal separation. So long as organic solvents dissolve theimpurities and not the compound (10), they are not restrictedspecifically, however,alcohols such as methanol, ethanol, andisopropylalcohol, and aromatic hydrocarbons such as toluene and xyleneare preffered. No particular restriction is imposed on the extractiontime; any length of time may be used in order to ensure efficientremoval of impurities, and preferably in the range of 1 to 5 hours. Norestriction is imposed on the extraction temperature; any temperaturemay be used in order to ensure efficient removal of impurities, andpreferably 10 to 150° C., more preferably, 10 to 50° C. and mostpreferably 10 to 40° C. A higher purity can be achieved throughrepetition of the impurity extraction procedure using an organicsolvent.

Then, the preparing method of compound (1) from the compound (2) throughhydrolysis or transesterification in the presence of an acid or basiccatalyst is explained. For this object, the method as described on pp.150 to 157 of “Protection for the Hydroxyl Group, Including 1,2-and1,3-Diols. In PROTECTIVE GROUPS IN ORGANIC SYNTHESIS—3^(rd) Ed.; T. W.Greene and P. G. M. Wuts Eds; John Wiley & Sons, Inc. 1999.” can beadopted. Said literature states on pp. 712 to 713 that the reactionproceeds under both acidic and basic conditions.

In transesterification or hydrolysis using a compound (2), preferably,the compound (2) is dissolved evenly or the main product (1) isdissolved according to the reaction progress. Specifically, intransesterification or hydrolysis using a compound (10) or (11), morepreferably, the compound (2) is dissolved evenly or a silsesquioxanecompound having hydroxyl groups prepared from each raw material isevenly dissolved according to the reaction progress. Solvents in whichthe above-described reaction proceeds efficiently are, though notrestricted specifically, alcohols, more preferably ethanol and methanol,and most preferably, methanol.

It is preferable that transesterification or hydrolysis is conductedusing a regulator that does not inhibit these reactions and is able todissolve the compound (2). The regulator should be a solvent. Examplesof the solvent include, though not restricted specifically,hydrochlorofluorocarbon solvents (HCFC-141b and HCFC-225),hydrofluorocarbon (HFCs) solvents (HFCs of at least two carbons),perfluorocarbon solvents (perfluoropentane and perfluorohexane),alicyclic hydrofluorocarbon solvents (fluorocyclopentane andfluorocyclobutane), oxygen-containing fluorinated solvents (fluoroether,fluoropolyether, fluoroketone, and fluoroalcohol), chloroform,methylenechloride and orthodichlorobenzne.

No particular restriction is imposed on the ratio of a regulator to analcohol; any ratio may be used so long as quantitativetransesterification or hydrolysis proceeds. For example, in achloroform/methanol solvent, the ratio, chloroform/methanol (volumeratio), should be preferably 1/1, 2/3 or 3/2, and most preferably 1/1.

No particular restriction is imposed on the reaction temperature; anytemperature may be used so long as quantitative transesterification orhydrolysis proceeds without any side reactions: a preferred range is 0to 100° C., and more preferably 20 to 40° C. No particular restrictionis imposed on the reaction time; any time may be used in order to ensurethat quantitative transesterification or hydrolysis proceeds. Usually,the desired silicon compound is obtained during 24 to 100 hours.

No particular restriction is imposed on the type of acidic or basiccatalyst employed in the invention; any catalyst may be used so long asquantitative transesterification or hydrolysis proceeds. Examples of thecatalyst include critic acid monohydrate, sodium hydrogen-carbonate,potassium carbonate, potassium prussiate, guanidine, ammonia, BF₃, HBF₄,p-toluene sulfonate, hydrochloric acid and sulfuric acid, and mostpreferably sulfuric acid. No particular restriction is imposed on thecatalyst content of a solvent. For example, in achloroform/methanol/sulfonic acid solvent, the sulfuric acid content ofthe solvent should be preferably in the range of 0.1 to 5 percent byweight, more preferably 0.1 to 1.0 percent by weight, or most preferably0.1 to 0.5 percent by weight.

Therefore, as the production process for silsesquioxane having hydroxylgroups from a compound (10) or (11), the method of transesterificationusing a chloroform/methanol/sulfonic acid solvent is most preferable,though not restricted to it. The silsesquioxane compound having hydroxylgroups thus obtained is purified by said purification method throughrecrystallization and said extraction method of impurities using anorganic solvent.

EXAMPLES

Hereinafter, the invention is further explained by means of a series ofexamples, however,which do not limit the scope of the invention.

The following is a list of symbols used in the invention and theirmeanings.

-   Ph: Phenyl-   Ch: Cyclohexyl-   Cp: Cyclopentyl-   Et: Ethyl-   iBu: Isobutyl-   iOc: Isooctyl-   TFPr: Trifluoropropyl-   TDFOc: Tridecafluoro-1,1,2,2-tetrahydrooctyl-   TMS: Trimethylsilyl-   Mn: Number-average molecular weight-   Mw: Weight-average molecular weight

Example 1

<Preparation of Polyphenylsilsesquioxane (Compound A)>

Ice water (640.7 g) and toluene (200 g) were placed into a 2-literfour-necked separable flask equipped with a stirrer, a reflux condenser,a thermometer and a dropping funnel, and then lowered the insidetemperature to 0° C. with stirring. A mixture of phenyltrichlorosilane(211.5 g) and toluene (130 g) dehydrated overnight with molecular sieveswas transferred into the dropping funnel and added dropwise for one hourat the rate to prevent the internal temperature of the flask not toexceed 2° C. After the contents was stirred at room temperature for 30minutes, the resulting product was washed with purified water. Toluenewas removed under reduced pressure to obtain a solid compound A (120.7g) with a weight-average molecular weight of approximately 3100.

<Preparation of Sodium-Bond Phenylsilsesquioxane Compound (Compound B)>

The compound A obtained above (12.9 g), tetrahydrofuran dehydratedovernight with molecular sieves (250 mL), and sodium hydroxide (4.0 g)were placed into a 500-mL four-necked flask equipped with a refluxcondenser and a thermometer. The mixture was stirred and heated at 67°C. under reflux. After four hours of reflux, a minute amount of powderwas precipitated and the solution began to exhibit a white turbidity.After another hours of reflux, the reaction was completed. Theprecipitate was washed with tetrahydrofuran, filtered and dried undervacuum to obtain a compound B (10.1 g).

Example 2

<Introduction of Trimethylsilyl Groups into a Compound B (Compound C)>

The compound B prepared in example 1 (2.0 g), toluene (100 g),triethylamine (1.7 g) and trimethylchlorosilane (1.4 g) were placed to a200-ml four-necked flask equipped with a reflux condenser, and stirredwith a magnetic stirrer at room temperature for two hours. After thereaction was completed, the resulting product was washed with purifiedwater and dried under vacuum to obtain a compound C (2.1 g).

The structure of compound C was analyzed by ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR,mass spectroscopy, X-ray and IR The ¹H-NMR and ¹³C-NMR data revealed theintegral ratio of phenyl groups to trimethylsilyl was 7:3. The ²⁹Si-NMRdata revealed a single peak which suggested trimethylsilyl groups at11.547 ppm, and three peaks that suggested a T-structure containing aphenyl group at −77.574 ppm, −78.137 ppm, and −78.424 ppm (relative totrimethylsilane) with an integral ratio of 1:3:3. The mass spectroscopyspectrum revealed that the absolute molecular weight matched with thetheoretical value of the structure of formula (103). The X-ray crystalstructure analysis found that the resulting compound C exhibited thestructure of formula (103). The IR spectrum found an absorption bandassigned to Si-Ph bending vibration at 1430 and 1590 cm⁻¹, an absorptionband assigned to harmonic of a substituted benzene ring at 1960 to 1760cm⁻¹, an absorption band assigned to Si—O—Si stretching vibration at1200 to 950 cm⁻¹, and an absorption band assigned to Si—CH₃ vibration at1250 cm⁻¹. These results corroborate the formation of a compoundsubstituted with trimethylsilyl groups (compound C) with a structure offormula (103) and suggests that the sodium-bound phenylsilsesquioxanecompound obtained (compound B) has a structure of formula (104). TheT-structure means a structure where three oxygen atoms are bound to anSi atom.

Example 3

<Preparation of Sodium-Bound Phenylsilsesquioxane Compound (Compound B)from Phenyltrimethoxysilane>

Phenyltrimethoxysilane (99 g), sodium hydroxide (10 g) and 2-propanol(500 ml) were placed into a 1-L four-necked flask equipped with astirrer bar, a reflux condenser, a thermometer, and a dropping funnel.The mixture was stirred with a magnetic stirrer at room temperature anddeionized water (11 g) was added dropwise from the dropping 10 funnelover two minutes. The flask was heated in an oil bath to the refluxingtemperature of 2-propanol. After 1.5 hours of reflux, the reaction wascompleted The flask was removed from the oil bath and allowed to standat room temperature overnight to fully crystallize the precipitate. Thecrystallized solid was filtered though a 0.1-μm membrane filer using apressure filtration equipment The solid obtained was washed once with2-propanol, and dried under reduced pressure at 70° C. for four hours toobtain a white solid (compound B, 66 g).

Example 4

<Introduction of Trimethyl Groups into a Compound B Prepared fromPhenyltrimethoxysilane (Compound C)>

The compound B prepared in Example 3 (1.2 g), tetrahydrofuran (12 g),and triethylamine (1.8 g) were placed into a 50-mL four-necked flaskequipped a stirrer bar, with a dropping funnel, a reflux condenser and athermometer. The apparatus was purged with dry nitrogen and sealed. Thereactants were stirred with the magnetic stirrer andchlorotrimethylsilane (2.3 g) was added dropwise from the droppingfunnel at room temperature over approximately one minute. Aftercompletion of the addition, the content was stirred for another threehours to complete the reaction. Pure water (10 g) was added to hydrolyzethe resulting sodium chloride and unreacted chlorotrimethylsilane. Theresulting mixture was transferred into a separating flask and the waterlayer was removed. The organic layer remaining inside was repeatedlywashed with deionized water until the washing water became neutral. Theorganic layer obtained was dehydrated with magnesium sulfate anhydride.The desiccant was removed by filtration, and the filtrate wasconcentrated under reduced pressure with a rotary evaporator to obtain awhite solid (compound C, 1.2 g).

The structure of the compound C was analyzed by ¹H-NMR, ¹³C-NMR,²⁹Si-NMR, mass spectroscopy, X-ray and IR. ¹H-NMR and ¹³C-NMR datarevealed the integral ratio of phenyl groups to trimethylsilyl groupswas 7:3. The ²⁹Si-NMR data revealed a peak that suggested trimethylgroups at 11.547 ppm, and three peaks that suggested a T-structurecontaining a phenyl group at −77.574 ppm, −78.137 ppm, and −78.424 ppm(relative to trimethylsilane) in an integral ratio of 1:3:3. The massspectroscopy spectrum showed that the absolute molecular weight matchedwith the theoretical value of the structure of said formula (103). TheX-ray crystal structure analysis found that the compound C had thestructure of said formula (103). The IR analysis found an absorptionband assigned to Si-Ph bending vibration at 1430 and 1590 cm⁻¹, anabsorption band assigned to harmonic of a substituted benzene ring at1960 to 1760 cm⁻¹, an absorption band assigned to Si—O—Si stretchingvibration at 1200 to 950 cm⁻¹, and an absorption band assigned to Si—CH₃at 1250 cm⁻¹. These analytical results corroborate formation of acompound prepared through the substitution of trimethylsilyl groups(compound C) with the structure of said formula (103) and suggests thatthe resulting sodium-bound phenylsilsesquioxane compound (compound B)has the structure of said formula (104). The T-structure means astructure where three oxygen atoms are bound to a Si atom.

Example 5

<Preparation of a Sodium-Bound Cyclohexylsilsesquioxane Compound fromCyclohexyltrimethoxysilane>

A sodium-bound cyclohexylsilsesquioxane compound-represented by formula(105) can be prepared as in Example 3 except-that in place ofphenyltrimethoxysilane, cyclohexyltrimethoxysilane is used.

Example 6

<Introduction of Trimethylsilyl Groups into a Compound (105)>

A silsesquioxane compound of formula (106) having trimethylsilyl groupscan be prepared as in Example 4 except that in place of compound (104),a compound (105) is used. The production of said compound (105) can beverified through the structural analysis of a compound (106) as inExample 4.

Example 7

<Preparation of a Sodium-Bound Cyclopentylsilsesquioxane Compound fromCyclopentyltrimethoxysilane>

Cyclopentyltrimethylsilane (19.0 g), tetrahydrofuran (THF) (100 mL),sodium hydroxide (1.7 g), and deionized water (2.3 g) were placed into a200-mL four-necked flask equipped with a reflux condenser, a thermometerand a dropping funnel. The reactants were stirred with a magneticstirrer and the flask was heated in an oil bath to the refluxingtemperature of 67° C. After ten hours of reflux with stirring, thereaction was completed. The flask was removed from the oil bath andallowed to stand at room temperature overnight to fully crystallize theprecipitate. The resulting solid was filtered off and dried under vacuumto obtain a powder solid (4.2 g).

Example 8

<Introduction of Trimethylsilane Groups>

The compound prepared in example 7 (1.0 g), tetrahydrofuran (30 mL),triethylamine (0.5 g), and trimethylchlorosilane (0.7 g) were placedinto a 100-mL four-necked flask equipped with a reflux condenser. Thereactants were stirred with a magnetic stirrer at room temperature fortwo hours. After the reaction was completed, treatment procedures wereapplied as in example 4, and a powdery solid (0.9 g) was obtained.

The structure of the resulting product was analyzed by ¹H-NMR, ²⁹Si-NMRand X-ray. The ¹H-NMR data revealed the integral ratio of cyclopentylgroups to trimethyl groups was 7:3. The ²⁹Si-NMR data revealed a peakthat suggested trimethyl groups at 8.43 ppm, and three peaks thatsuggested a T-structure containing cyclopentyl groups at −66.37 ppm,−67.97 ppm and −67.99 ppm. The ratio of the intensity of a sum of the−67.97 ppm and −67.99 ppm peaks to that of the −66.37 ppm peak was 6:1.These results combined with the crystal structure obtained through X-rayanalysis indicate that the compounds of the powdery solid are of thesilicon compound represented by formula (107). This suggests that thecompound obtained in example 7 has the structure represented by formula(108).

Example 9

<Preparation of a Sodium-Bound Ethylsilsesquioxane Compound fromEthyltrimethoxysilane>

A sodium-bound ethylsilsesquioxane compound represented by formula (109)can be prepared as in example 3 except that in place ofphenyltrimethoxysilane, ethyltrimethoxysilane is used.

Example 10

<Introduction of Trimethylsilyl Groups into a Compound (109)>

An ethylsilsesquioxane compound represented by formula (110) can beprepared as in example 4 except that in place of compound (104), acompound (109) is used. The production of said compound (109) can beverified by conducting structure analyses of the compound (110) as inexample 4.

Example 11

<Preparation of a Sodium-Bound Isobutylsilsesquioxane Compound fromIsobutyltrimethoxysilane>

Isobutyltrimethoxysilane (18.7 g), tetrahydrofuran (100 mL), sodiumhydroxide (1.8 g) and deionized water (2.4 g) were placed into a 200-mLfour-necked flask equipped with a reflux condenser, a thermometer, and adropping funnel. The reactants were stirred and heated to the refluxingtemperature of 67° C. After ten hours of reflux with stirring, thereaction was completed. The resulting liquid was concentrated atconstant pressure until precipitation of a solid had just beeninitiated. The resulting product was allowed to stand at roomtemperature overnight to fully precipitate the solid. The solid obtainedwas filtered off and then dried under vacuum to obtain a powdery solid(5.1 g).

Example 12

<Introduction of Trimethylsilyl Groups>

The powdery solid prepared in example 11 (1.0 g), tetrahydrofuran (20mL), triethylamine (0.5 g) and trimethylsilane (0.8 g) were placed intoa 200-mL four-necked flask equipped with a reflux condenser. Thereactants were stirred with a magnetic stirrer at room temperature fortwo hours. After the reaction was completed, treatment procedures wereapplied as in example 4 to obtain a powdery solid (0.9 g).

The structure of the powdery product was analyzed by ¹H-NMR and ²⁹Si-NMRThe ¹H-NMR data revealed the integral ratio of isobutyl groups totrimethylsilyl groups to be 7:3. The ²⁹Si-NMR data revealed a peak thatsuggested trimethylsilyl groups at 8.72 ppm and three peaks thatsuggested a T-structure containing isobutyl groups at −67.38 ppm, −68.01ppm and −68.37 ppm at an integral ratio of 1:3:3. These results indicatethat the powdery compound is of the silicon compound represented byformula (111) and suggests that the compound prepared in example 11 hasthe structure represented by formula (112).

Example 13

<Preparation of a Sodium-Bound Isooctylsilsesquioxane Compound fromIsooctyltrimethoxysilane>

A sodium-bound isooctylsilsesquioxane compound represented by formula(113) can be prepared as in example 3 except that in place ofphenyltrimethoxysilane, isooctyltrimethoxysilane is used.

Example 14

<Introduction of Trimethylsilyl Groups into a Compound (113)>

An isooctylsilsesquioxane compound represented by formula (114) can beprepared as in example 4 except that in place of compound (104), acompound (113) is used. The product of said compound (113) can beverified by conducting structure analyses of the compound (114) as inexample 4.

Example 15

<Preparation of a Sodium-Bound Trifluoropropylsilsesquioxane Compoundfrom Tifluoropropyltrimethoxysilane>

Trifluoropropyltrimethoxysilane (100 g), tetrahydrofuran (500 mL),deionized water (10.5 g) and sodium hydroxide (7.9 g) were placed into a1-L four-necked flask equipped with a reflux condenser, a thermometer,and a dropping funnel. The reactants were stirred with a magneticstirrer and the flask was heated in an oil bath to the refluxingtemperature of tetrahydrofuran. After five hours of reflux withstirring, the reaction was completed. The flask was removed from the oilbath and allowed to stand at room temperature overnight The flask wasplaced in the oil bath again, and the content was concentrated byheating at a constant pressure until the solid was fully precipitated.The precipitate was filtered off using a 0.5-μm membrane fitted to apressure filter. The resulting solid was washed once withtetrahydrofuran, and dried under reduced pressure and 80° C. for threehours to obtain a colorless powdery solid (74 g).

Example 16

<Introduction of Trimethylsilyl Groups>

The colorless powdery solid prepared in example 15 (1.0 g),tetrahydrofuran (10 g) and triethylamine (1.0 g) were placed into a50-mL four-necked flask equipped with a dropping funnel, a refluxcondenser, and a thermometer. The apparatus was purged with dry nitrogenand sealed. While the reactants were stirred with a magnetic stirrer,chlorotrimethylsilane (3.3 g) was added dropwise from the droppingfunnel at room temperature over one minute. On completion of theaddition, the content was stirred for another three hours to completethe reaction. Pure water (10 g) was added inside the flask to hydrolyzethe resulting sodium chloride and unreacted chlorotrimethylsilane. Theresulting mixture was transferred into a separating flask and the waterlayer was removed. The remaining organic layer was repeatedly washedwith deionized water until the washing solution became neutral. Theorganic layer obtained was dehydrated with magnesium sulfate anhydrideand the desiccant was removed by filtration. The filtrate wasconcentrated under reduced pressure with a rotary evaporator to obtain awhite solid (0.9 g).

The structure of the white solid analyzed by gel permeationchromatography (GPC), ¹H-NMR, ²⁹Si-NMR, ¹³C-NMR, mass spectroscopy andX-ray. The GPC data indicated that the resulting white powdery solid wasmonodispersed, exhibited a weight-average molecular weight relative topolystyrene standards of 1570 and had a purity of 98 percent by weight.The ¹H-NMR data revealed the integral ratio of trifluoropropyl groups totrimethylsilyl groups was 7:3. The ²⁹Si-NMR data revealed three peaksthat suggested a T-structure containing trifluoropropyl groups at anintegral ratio of 1:3:3, and a peak that suggested a trimethylsilylgroup at 12.11 ppm. The ¹³C-NMR data found peaks that suggestedtrifluoropropyl groups at 131 to 123 ppm, 28 to 27 ppm and 6 to 5 ppm,and a peak that suggested trimathylsilyl groups at 1.4 ppm. The massspectrogram showed that the absolute molecular weight matched with thetheoretical value of the structure with the formula (115). X-rayanalysis indicated that the sample had the structure represented byformula (115). These analytical results indicate that the white powderysolid had the structure represented by formula (115) and suggests thatthe compound before trimethylsilanization had the structure representedby formula (116).

Example 17

<Preparation of acetoxyethyl-heptaphenyloctasilsesquioxane from aCompound (104)>

The compound (104) prepared in example 1 (10 g) and tetrahydrofuran (200mL) were placed into a 500-mL four-necked flask equipped with a stirrerbar, a reflux condenser and a thermometer. Acetoxyethyltrichlorosilane(3.3 g, 1.5 equivalent of the compound (104)) was rapidly added to theflask contents and the reactants were stirred at room temperature fortwo hours. The resulting liquid was then transferred into hexane (1000g) and a solid was precipitated. The precipitate was filtered off undersuction and dissolved in toluene (90 g). The organic layer was washedthree times with water (330 mL) and dehydrated with magnesium sulfateanhydride (5 g). The desiccant was removed by filtration and thefiltrate was concentrated to yield a solid precipitate. Ethanol (90 g)was added to the precipitate and the mixture was stirred at roomtemperature. The solid was filtered off under pressure and dried underreduced pressure (80° C., three hours) to obtain a colorless solid (6.88g, yield: 65.9%).

Analysis by gel permeation chromatography of the resulting solidrevealed only a singlet peak, suggesting the exclusion of impurities.The following IR, ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR results show that thesolid exhibits the structure represented by formula (117).

IR (KBr tablet method): v=1740 (C═O), 1430 (Si-Ph), 1240 (C—O),1135-1090 (Si-Ph), 1090-1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 7.82-7.72, 7.46-7.31 (m, 35H,Ph-Si), 4.32-4.28 (t, 2H, —O—CH₂—), 1.84 (s, 3H, CH₃—(C═O)—), 1.37-1.33(t, 2H, —CH₂—Si)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 171.15 (C═O), 134.4-134.3,131.1-131.0, 130.2, 128.12 (Ph-Si), 60.6 (—O—CH₂—), 20.8 (CH₃—(C═O)—),13.2 (—CH₂—Si)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −67.97 (−CH₂—SiO_(1.5)),−78.36, −78.67 (Ph-SiO_(1.5))

Example 18

<Preparation of acetoxyethyl-heptacyclohexyloctasilsesquioxane from aCompound (105)>

A compound represented by formula (118) can be prepared as in example 17except that in place of compound (104), the compound (105) prepared inexample 5 is used.

Example 19

<Preparation of acetoxyethyl-heptacyclopentyloctasilsesquioxane from aCompound (108)>

A compound represented by formula (119) can be prepared as in example 17except that in place of compound (104), the compound (108) prepared inexample 7 is used.

Example 20

<Preparation of acetoxyethyl-heptaethyloctasilsesquioxane from aCompound (109)>

A compound represented by formula (120) can be prepared as in example 17except that in place of compound (104), the compound (109) prepared inexample 9 is used.

Example 21

<Preparation of acetoxyethyl-heptaisobutyloctasilsesquioxane from aCompound (112)>

A compound represented by formula (121) can be prepared as in example 17except that in-place of compound (104), the compound (112) prepared inexample 11 is used.

Example 22

<Preparation of acetoxyethyl-heptaisooctyloctasilsesquioxane from aCompound (113)>

A compound represented by formula (122) can be prepared as in example 17except that in place of compound (104), the compound (113) prepared inexample 13 is used.

Example 23

<Preparation of acetoxyethyl-heptatrifluoropropyloctasilsesquioxane froma Compound (116)>

The compound (116) prepared in example 15 (22.71 g) and tetrahydrofuran(400 g) were placed into a 500-mL four-necked flask equipped with astirrer bar, a reflux condenser, a thermometer.Acetoxyethyltrichlorosilane (3.21 g, 1.6 equivalent of the compound(104)) was rapidly added to the flask contents and the reactants werestirred at room temperature for four hours. The reaction mixture wasfiltered off, and the filtrate was concentrated with a rotaryevaporator. Methanol (100 mL) was added to the condensate, and theresulting solid was filtered off. Tetrahydrofuran (200 mL) was added tothe solid and the solution was dehydrated with magnesium sulfateanhydride (5 g). The desiccant was removed by filtration and thefiltrate was concentrated to yield a solid. Methanol (100 g) was addedto the solid and stirred at room temperature. The solid was filtered offand dried under reduced pressure at 75° C. for five hours to obtain acolorless solid (12.2 g, yield: 51.6%).

Analysis of the solid by gel permeation chromatography revealed only asinglet peak, suggesting the exclusion of impurities. The following IR,¹H-NMR, ¹³C-NMR, and ²⁹Si-NMR results show that the colorless solidexhibits the structure represented by formula (123).

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 4.18 (t, 2H, —O—CH₂—), 2.14(m, 14H, —[CH₂]—CF₃), 2.04 (s, 3H, CH₃—(C═O)—), 1.19 (t, 2H, —CH₂ —Si),0.95 (m, 14H, Si—[CH₂]—CH₂—CF₃)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 171.11 (C═O), 131.41,128.68, 125.92, 123.20 (—CF₃), 60.01 (—O—CH₂—), 28.17, 27.85, 27.55,27.25 (—[CH₂]—CF₃), 20.92 (CH₃—(C═O)—), 12.81 (—CH₂—Si), 4.03(Si—[CH₂]—CH₂—CF₃)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −68.66 (—CH₂—SiO_(1.5)),−67.62, −67.72 (CF₃—CH₂—CH₂—SiO_(1.5))

Example 24

<Preparation of acetoxyethyl-heptaphenyloctasilsesquioxane from aCompound (124)>

A compound of formula (124) (10 g, trisilanolphenyl-POSS, HybridPlastics, U.S.), triethylamine (4.24 g, 1.3 equivalent of silanol), andtetrahydrofuran (200 mL) were placed into a 500-mL four-necked flaskequipped with a stirrer bar, a dropping funnel, a reflux condenser, anda thermometer and immersed in an ice bath. Acetoxyethyltrichlorosilane(3.32 g, 1.5 equivalent of the compound (124)) was rapidly added to theflask contents and the reactants were stirred at room temperature fortwo hours. The resulting liquid was transferred into hexane (1000 g),and a solid was formed. The solid was filtered off under suction andthen dissolved in toluene (90 g). The organic layer was washed threetimes with water (330 mL) and dehydrated with magnesium sulfateanhydride (5 g). The desiccant was removed by filtration. Ethanol (90 g)was added to the solid obtained through concentration of the filtrate,and the mixture was stirred at room temperature. The remaining solid wasfiltered off and dried under vacuum at 80° C. for three hours to obtaina colorless solid (5.25 g, yield: 47.0%).

Analysis by gel permeation chromatography of the colorless solidrevealed only a singlet peak, suggesting the exclusion of impurities.The following IR, ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR results show that thecolorless solid exhibits the structure represented by formula (117).

IR (KBr tablet method): v=1740 (C═O), 1430 (Si-Ph), 1240 (C—O),1135-1090 (Si-Ph), 1090-1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 7.82-7.72, 7.46-7.31 (m, 35H,Ph-Si), 4.32-4.28 (t, 2H, —O—CH₂—), 1.84 (s, 3H, CH₃—(C═O)—), 1.37-1.33(t, 2H, —CH₂—Si)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 171.15 (C═O), 134.4-134.3,131.1-131.0, 130.2, 128.12 (Ph-Si), 60.6 (—O—CH₂—), 20.8 (CH₃—(C═O)—),13.2 (—CH₂—Si)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −67.97 (—CH₂—SiO_(1.5)),−78.36, −78.67 (Ph-SiO—_(1.5))

Example 25

<Preparation of acetoxyethyl-heptacyclohexyloctasilsesquioxane from aCompound (125)

The compound (118) described in example 18 can be prepared as in example24 except that in place of compound (124), a compound represented byformula (125)>(trisilanolcyclohexyl-POSS, Hybrid Plastics, U.S.) isused.

Example 26

<Preparation of acetoxyethyl-heptacyclopentyloctasilsesquioxane form aCompound (126)>

The compound (119) described in example 19 can be prepared as in example24 except that in place of compound (124), a compound represented byformula (126) (trisilanolcyclopentyl-POSS, Hybrid Plastics, U.S.) isused.

Example 27

<Preparation of acetoxyethyl-heptaethyloctasilsesquioxane from aCompound (127)>

The compound (120) described in example 20 can be prepared as in example24 except that in place of compound (124), a compound represented byformula (127) (trisilanolethyl-POSS, Hybrid Plastics, U.S.) is used.

Example 28

<Preparation of acetoxyethyl-heptaisobutyloctasilsesquioxane from aCompound (128)>

The compound (121) described in example 21 can be prepared as in example24 10 except that in place of compound (124), a compound represented byformula (128) (trisilanolisobutyl-POSS, Hybrid Plastics, U.S.) is used.

Example 29

<Preparation of acetoxyethyl-heptaisooctyloctasilsesquioxane from aCompound (129)>

The compound (122) described in example 22 can be prepared as in example24 except that in place of compound (124), a compound represented byformula (129) (trisilanolisooctyl-POSS, Hybrid Plastics, U.S.) is used.

Example 30

<Preparation of a Silanol-Containing HeptatrifluoropropylsilsesquioxaneCompound from a Compound (116)>

The compound (116) prepared in example 15 (5 g) was placed into a 300-mLfour-necked flask equipped with a stirrer bar, a dropping funnel, areflux condenser, and a thermometer and immersed in an ice bath. Butylacetate (50 g) was added to the flask contents to dissolve the compound.Acetic acid (0.5 g) was added dropwise, and the reactants were stirredin the ice bath for one hour. The flask was removed from the bath, andallowed to stand to room temperature. The resulting liquid was washedthree times with deionized water (100 mL). The solvent was removed witha rotary evaporator and the resulting product was dried under reducedpressure at 50° C. for one hour to obtain a glutinous liquid (4.3 g).

Analysis of the resulting compound by gel permeation chromatographyrevealed only a singlet peak, suggesting the exclusion of impurities. AnIR analysis of the compound revealed existence of an absorption band (atand around 3400 cm⁻¹) that suggests the presence of silanol groups whichwere not observed in the IR data of compound (116). These resultssuggest that the resulting compound exhibits the structure representedby formula (130).

<Preparation of acetoxyethyl-heptatrifluoropropyloctasilsesquioxane froma Compound (130)>

A compound (123) can be prepared by reacting acetoxyethyltrichlorosilanewith compound (130) in the presence of triethylamine as in examples 24to 29.

Example 31

<Preparation of a Raw Material ofacetoxypropyl-heptaphenyloctasilsesquioxane from a Compound (104)>

The compound (104) prepared in example 1 (10 g), triethylamine (1.5 g)and tetrahydrofuran (200 mL) were placed into a 500-mL four-necked flaskequipped with a stirrer bar, a reflux condenser and a thermometer.Acetoxypropyltrichlorosilane (3.5 g, 1.5 equivalent of the compound(104)) was added to the flask contents and the reactants were stirred atroom temperature for two hours. The resulting liquid was added intohexane (1000 g) and a solid was precipitated. The precipitate wasfiltered off under suction and dissolved in toluene (90 g). The organiclayer was washed three times-with water (330 mL) and dehydrated withmagnesium sulfate anhydride (5 g). The desiccant was removed byfiltration. The filtrate was concentrated to obtain a solid. Ethanol (90g) was added to the solid and the mixture was stirred at roomtemperature. The solid was filtered off under pressure and dried underreduced pressure at 80° C. for three hours to obtain a colorless solid(7.15 g, yield: 67.6%).

Analysis of the resulting product by gel permeation chromatographyrevealed only a singlet peak, suggesting the exclusion of impurities.The following IR, ¹H-NMR, ¹³C-NMR, and ²⁹Si-NMR results show that thesolid exhibits the structure represented by formula (131).

IR (KBr tablet method): v=1740 (C═O), 1430 (Si-Ph), 1240 (C—O),1135-1090 (Si-Ph), 1090-1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 7.82-7.72, 7.46-7.31 (m, 35H,[Ph]-Si), 4.07-4.04 (t, 2H, —O—[CH₂]—), 1.94 (s, 3H, [CH₃]—(C═O)—),1.84-1.88 (tt, 2H, —CH₂—[CH₂]—CH₂—), 1.37-1.33 (t, 2H, —[CH₂]—Si)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 171.10 (C═O), 134.4-134.3,131.1-131.0, 130.2, 128.12 (Ph-Si), 66.2 (—O—CH₂—), 22.2(—CH₂—[CH₂]—CH₂—), 20.9 ([CH₃]—(C═O)—), 8.26 (—[CH₂]—Si)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −65.30 (—CH₂—SiO_(1.5))−78.26, −78.62 (Ph-SiO_(1.5))

Example 32

<Preparation of acetoxypropyl-heptacyclohexyloctasilsesquioxane from aCompound (105)>

A compound represented by formula (132) can be prepared as in example 31except that in place of compound (104), the compound (105) prepared inexample 5 is used.

Example 33

<Preparation of acetoxypropyl-heptacyclopentyloctasilsesquioxane from aCompound (108)>

A compound represented by formula (133) can be prepared as in example 31except that in place of compound (104), the compound (108) prepared inexample 7 is used.

Example 34

<Preparation of acetoxypropyl-heptaethyloctasilsesquioxane from aCompound (109)>

A compound represented by formula (134) can be prepared as in example 31except that in place of compound (104), the compound (109) prepared inexample 9 is used.

Example 35

<Preparation of acetoxypropyl-heptaisobutyloctasilsesquioxane from aCompound (112)>

A compound represented by formula (135) can be prepared as in example 31except that in place of compound (104), the compound (112) prepared inexample 11 is used.

Example 36

<Preparation of acetoxypropyl-heptaisooctyloctasilsesquioxane from aCompound (113)>

A compound represented by formula (136) can be prepared as in example 31except that in place of compound (104), the compound (113) prepared inexample 13 is used.

Example 37

<Preparation of acetoxypropyl-heptatrifluoropropyloctasilsesquioxaneform a Compound (116)>

A compound represented by formula (137) can be prepared according to thereaction conditions described in example 31 and purification conditionsdescribed in example 23 except that in place of compound (104), thecompound (116) prepared in example 15 is used.

Example 38

<Preparation of acetoxypropyl-heptaphenyloctasilsesquioxane from aCompound (124)>

The compound (131).described in example 31 can be prepared by reacting acompound represented by formula (124) (trisilanolphenyl-POSS, HybridPlastics, U.S.) described in example 24 withacetoxypropyltrichlorosilane (1.5 equivalent of a compound (124)) intetrahydrofuran in the presence of triethylamine (1.3 equivalent ofsilanol).

Example 39

<Preparation of acetoxypropyl-heptacyclohexyloctasilsesquioxane from aCompound (125)>

A compound (132) described in example 32 can be prepared as in example38 except that in place of compound (124), a compound represented byformula (125) (trisilanolcyclohexyl-POSS, Hybrid Plastics, U.S.) isused.

Example 40

<Preparation of acetoxypropyl-heptacyclopentyloctasilsesquioxane from aCompound (126)>

The compound (133) described in example 33 can be prepared as in example38 except that in place of compound (124), a compound represented byformula (126) (trisilanolcyclopentyl-POSS, Hybrid Plastics, U.S.) isused.

Example 41

<Preparation of acetoxypropyl-heptaethyloctasilsesquioxane from aCompound (127)>

The compound (134) described in example 34 can be prepared as in example38 except that in place of compound (124), a compound represented byformula (127) (trisilanolethyl-POSS, Hybrid Plastics, U.S.) is used.

Example 42

<Preparation of acetoxypropyl-heptaisobutyloctasilsesquioxane from aCompound (128)>

The compound (135) described in example 35 can be prepared as in example38 except that in place of compound (124), a compound represented byformula (128) (trisilanolisobutyl-POSS, Hybrid Plastics, U.S.) is used.

Example 43

<Preparation of acetoxypropyl-heptaisooctyloctasilsesquioxane from aCompound (129)>

The compound (136) described in example 36 can be prepared as in example38 except that in place of compound (124), a compound represented byformula (129) (trisilanolisooctyl-POSS, Hybrid Plastics, U.S.) is used.

Example 44

<Preparation of acetoxypropyl-heptatrifluoropropyloctasilsesquioxaneform a Compound (130)>

The compound (137) described in example 37 can be prepared by reactingacetoxyethyltrichlorosilane in the presence of triethylamine as inexamples 31 to 43 except that in place of compound (124), a compoundrepresented by formula (130) is used.

Example 45

<Preparation of hydroxyethyl-heptaphenyloctasilsesquioxane from aCompound (117)>

The compound (117) prepared in example 17 (2.58 g) was placed into a500-mL round-bottom flask containing a stirring bar. A mixed solution(300 mL) of methanol (174.7 mL), chloroform (174.3 mL) and sulfuric acid(36N, 0.7 mL) were added into the flask, and the reactants were stirredat room temperature for 72 hours. The resulting solution wasconcentrated with a rotary evaporator, and the concentrate was dissolvedin ethyl acetate (500 mL). The organic layer was washed with water (500mL) in a separating funnel, and dehydrated with magnesium sulfateanhydride (5 g). The desiccant was removed by filtration and thefiltrate was concentrated with a rotary evaporator. The concentrate wasdried and a colorless solid (2.37 g, yield: 91.7%) was obtained. Thesolid (1.09 g) was recrystallized in toluene. The solvent was removedunder reduced pressure to obtain a colorless solid (0.48 g, yield:43.7%).

Analysis of the resulting product by gel permeation chromatographyrevealed only a singlet peak, indicating the exclusion of impurities.The following IR, ¹H-NMR, ¹³C-NMR, and ²⁹Si-NMR results show that theproduct exhibits the structure represented by formula (138).

IR (KBr tablet method): v=3600-3200 (OH), 1420 (Si-Ph), 1135-1090(Si-Ph), 1090-1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 7.82-7.72, 7.46-7.31 (m, 35H,Ph-Si), 3.85-3.87 (t, 2H, —CH₂—O—), 1.42-1.62 (broad, 1H, —OH),1.26-1.31 (t, 2H, Si—CH₂—)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 134.5-134.1, 131.1-131.0,130.3, 128.11-127.9 (Ph-Si), 58.6 (—CH₂—OH), 17.5 (Si—CH₂—)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −67.31 (—CH₂—SiO_(1.5)),−78.42, −78.79 (Ph-SiO_(1.5))

The compound (138) prepared in example 24 can be derived from compound(117) according to the above procedures.

Example 46

<Preparation of hydroxyethyl-heptaphenyloctasilsesquioxane from aCompound (117)>

A colorless solid (0.09 g, yield: 94.7%) was obtained through reactionconducted as in example 2 except that the reactants were replaced bycompound (117) prepared in example 17 (0.1 g), methanol (66.6 mL),chloroform (100 mL), and sulfuric acid (36N, 0.3 mL). A colorless solid(0.09 g, yield: 94.7%) was obtained. The following IR, ¹H-NMR, ¹³C-NMR,and ²⁹Si-NMR results show that the resulting product exhibits thestructure represented by formula (138).

IR (KBr tablet method): v=3600-3200 (OH), 1420 (Si-Ph), 1135-1090(Si-Ph), 1090-1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 7.82-7.72, 7.46-7.31 (m, 35H,Ph-Si), 3.85-3.87 (t, 2H, —CH₂—O—), 1.42-1.62 (broad, 1H, —OH),1.26-1.31 (t, 2H, Si—CH₂—)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 134.5-134.1, 131.1-131.0,130.3, 128.11-127.9 (Ph-Si), 58.6 (—CH₂—OH), 17.5 (Si—CH₂—)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −67.31 (—CH₂—SiO_(1.5)),−78.42, −78.79 (Ph-SiO_(1.5))

The compound (138) prepared in example 24 can be derived from a compound(117) according to the above procedures.

Example 47

<Transesterification of a Compound (117) in Chloroform/Methanol/SulfuricAcid>

A colorless solid (0.064 g, yield: 67.4%) was obtained through areaction conducted as in example 2 except that the reactants werereplaced by compound (117) prepared in example 17 (0.1 g), ethanol (83.3mL), chloroform (83.3 mL), and sulfuric acid (36 N, 0.3 mL). IR analysisof the resulting product revealed the existence of an absorption bandthat suggested an acetoxy group at 1740 cm⁻¹. ¹H-NMR analysis revealedthat the product consists of a compound (138) and the compound (117)(content of compound (138): 66.3 mol %).

Example 48

<Transesterification of a Compound (117) in Chloroform/Methanol/SulfuricAcid>

A colorless solid (0.078 g, yield: 82.1%) was obtained through areaction conducted as in example 2 except that the reactants werereplaced by the compound (117) prepared in example 17 (0.1 g), ethanol(66.6 mL), chloroform (100 mL), and sulfuric acid (36 N, 0.3 mL), andthe reaction time was adjusted to 96 hours. IR analysis of the productrevealed the existence of an absorption band that suggested an acetoxygroup at 1740 cm⁻¹. ¹H-NMR analysis revealed the product consists of acompound (138) and the compound (117) (content of compound (138): 90.1mol %).

Example 49

<Preparation of hydroxyethyl-heptacyclohexyloctasilsesquioxane from aCompound (118)>

A compound represented by formula (139) can be prepared as in example 45except that in place of compound (117), the compound (118) prepared inexample 18 or 25 is used.

Example 50

<Preparation of hydroxyethyl-heptacyclopentyloctasilsesquioxane from aCompound (119)>

A compound represented by formula (140) can be prepared as in example 45except that in place of compound (117), the compound (119) prepared inexample 19 or 26 is used.

Example 51

<Preparation of hydroxyethyl-heptaethyloctasilsesquioxane from aCompound (120)>

A compound represented by formula (141) can be prepared as in example 45except that in place of compound (117), the compound (120) prepared inexample 20 or 27 is used.

Example 52

<Preparation of hydroxyethyl-heptaisobutyloctasilsesquioxane from aCompound (121)>

A compound represented by formula (142) can be prepared as in example 45except that in place of compound (117), the compound (121) prepared inexample 21 or 28 is used.

Example 53

<Preparation of hydroxyethyl-heptaisooctyloctasilsesquioxane from aCompound (122)>

A compound represented by formula (143) can be prepared as in example 45except that in place of compound (117), the compound (122) prepared inexample 22 or 29 is used.

Example 54

<Preparation of hydroxyethyl-heptatrifluoropropyloctasilsesquioxane froma Compound (123)

The compound (123) prepared in example 23 (3.5 g) was placed into a 1-Lthree-necked flask equipped with a stirrer bar, a reflux condenser, anda thermometer. A mixture of methanol (359.5 mL), AK-225 (HCFC-225:CF₃CF₂CHCl₂/CClF₂CF₂CHClF, 5 Asahi Glass Co., 239.6 mL), and sulfuricacid (36 N, 0.9 mL) was added to the flask contents and the reactantswere stirred at room temperature for 12 hours. The flask was heated to45° C. and the stirring was continued at that temperature for another 9hours. The resulting solution was concentrated with a rotary evaporator,and the concentrate was dissolved in AK-225 (200 mL). The organic layerwas washed with water (500 mL) in a separating flask, and dehydratedwith magnesium sulfate anhydride (5 g). The desiccant was removed byfiltration, the filtrate was condensed with a rotary evaporator, and thecondensate was dried to obtain a colorless solid (3.04 g, yield: 89.9%).

Analysis of the resulting product by gel permeation chromatographyrevealed only a singlet peak, indicating the exclusion of impurities.The following ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR results show that the productexhibits the structure represented by formula (144).

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 3.81 (t, 2H, —CH₂—O—), 2.14(m, 14H, —[CH₂]—CF₃), 1.39 (broad, 1H, —OH), 1.13 (t, 2H,Si—[CH₂]—CH₂—OH), 0.93 (m, 14H, Si—[CH₂]—CH₂—CF₃)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 131.31, 128.58, 125.83,123.11 (—CF₃), 58.08 (—CH₂—OH), 28.12, 27.83, 27.52, 27.22 (—[CH₂]—CF₃),19.74 (—CH₂—Si), 4.02 (Si—[CH₂]—CH₂—CF₃)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −67.84 (—CH₂—SiO_(1.5)),−67.65, −67.66, −67.84 (CF₃—CH₂—CH₂—SiO_(1.5))

A compound (144) can be derived from the compound (123) prepared inexample 30 according to the above procedures.

Example 55 Transesterification of a Compound (123) inChloroform/Methanol/Sulfuric Acid

A colorless solid (yield: 93.1%) was obtained through reaction conductedas in example 54 except that the reactants were replaced by the compound(123) prepared in example 23 (0.5 g), methanol (42.7 mL), AK-225 (42.7mL), and sulfuric acid (36 N, 0.26 mL). ¹H-NMR analysis revealed thatthe product consists of a compound (144) and the compound (123) (contentof compound (144): 89.4 mol %).

Example 56 Transesterification of a Compound (123) inChloroform/Methanol/Sulfuric Acid

A white solid (yield: 92.2%) was obtained through reaction conducted asin example 54 except that the reactants were replaced by the compound(123) prepared in example 23 (0.5 g), methanol (42.7 mL), AK-225 (42.7mL) and sulfuric acid (36 N, 0.26 mL), the reaction temperature waslowered to room temperature, and the reaction time was extended to 72hours. ¹H-NMR data showed that the product consisted of a compound (144)and the compound (123) (content of compound (144): 91.3 mol %).

Example 57 Transesterification of a Compound (123) inChloroform/Methanol/Sulfuric Acid

A colorless solid (yield: 91.0%) was obtained through reaction conductedas in example 54 except that the reactants were replaced by the compound(123) prepared in example 23 (0.5 g), methanol (42.7 mL), chloroform(42.7 mL) and sulfuric acid (36 N, 0.26 mL), the reaction temperaturewas lowered to room temperature, and the reaction time was extended to72 hours. ¹H-NMR data showed that the product consisted of a compound(144) and the compound (123) (content of compound (144): 81.5 mol %).

Example 58 Transesterification of a Compound (123) inChloroform/Methanol/Sulfuric Acid

A colorless solid (yield: 90.9%) was obtained through reaction conductedas in example 54 except that the reactants were replaced by the compound(123) prepared in example 23 (0.5 g), methanol (42.7 mL), chloroform(42.7 mL) and p-toluene sulfonate (4.43 g), the reaction temperature waslowered to room temperature and the reaction time was extended to 72hours. ¹H-NMR data showed that the product consisted of a compound (144)and the compound (123) (content of compound (144): 89.0 mol %).

Example 59 Preparation of hydroxypropyl-heptaphenyloctasilsesquioxanefrom a Compound (131)

The compound (131) prepared in example 31 (2.5 g), and a mixed solution(417.4 mL) of methanol (208.3 mL), chloroform (208.3 mL) and sulfuricacid (36 N, 0.75 mL) were placed into a 500-mL round-bottom flaskcontaining a stirring bar. The reactants were stirred at roomtemperature for 72 hours. The resulting liquid was concentrated with arotary evaporator. The condensate was dissolved in ethyl acetate (500mL). The organic layer was washed with water (500 mL) in a separatingfunnel and dehydrated with magnesium sulfate anhydride (5.0 g). Afterthe desiccant was removed by filtration, the filtrate was concentratedwith a rotary evaporator to yield a solid. The solid was dried to obtaina colorless solid (2.35 g, yield: 97.9%). The solid was washed withethanol and the washing solution removed through suction filtration toobtain a colorless solid (compound G) (1.26 g, yield: 52.5%).

Analysis of the resulting product by gel permeation chromatographyrevealed only a singlet peak, indicating the exclusion of impurities.The following IR, ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR results show that theproduct exhibits the structure represented by formula (145).

IR (KBr tablet method): v=3600-3200 (OH), 1420 (Si-Ph), 1135-1090(Si-Ph), 1090-1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS-standard: δ=0.0 ppm): 7.82-7.72, 7.48-7.32 (m, 35H,[Ph]-Si), 3.62-3.57 (t, 2H, —[CH₂]-0-), 1.2 (broad, 1H, —[OH], 1.78-1.74(tt, 2H, —CH₂—[CH₂]—CH₂—), 0.90-0.86 (t, 2H, Si—[CH₂]—)

¹³C NMR (100 MHz, TMS-standard: δ=0.0 ppm): 134.5-134.4, 131.1-131.0,130.6-130.4, 128.2-128.1 ([Ph]-Si), 65.0 (—[CH₂]—OH), 26.1(—CH₂—[CH₂]—CH₂—), 7.9 (Si—[CH₂]—)

²⁹Si NMR (79 MHz, TMS-standard: δ=0.0 ppm): −65.08 (—CH₂—SiO_(1.5)),−78.55, −78.94 (Ph-SiO_(1.5))

A compound (145) can be derived from the compound (131) prepared inexample 38 according to the above procedures.

Example 60 Preparation ofhydroxypropyl-heptacyclohexyloctasilsesquioxane from a Compound (132)

A compound represented by formula (146) can be prepared as in example 59except that in place of compound (131), the compound (132) prepared inexample 32 or 39 is used.

Example 61 Preparation ofhydroxypropyl-heptacyclopentyloctasilsesquioxane from a Compound (133)

A compound represented by formula (147) can be prepared as in example 59except that in place of compound (131), the compound (133) prepared inexample 33 or 40 is used.

Example 62 Preparation of hydroxypropyl-heptaethyloctasilsesquioxanefrom a Compound (134)

A compound represented by formula (148) can be prepared as in example 45except that in place of compound (131), the compound (134) prepared inexample 34 or 41 is used.

Example 63 Preparation of hydroxypropyl-heptaisobutyloctasilsesquioxanefrom a Compound (135)

A compound represented by formula (149) can be obtained as in example 45except that in place of compound (131), the compound (135) prepared inexample 35 or 42 is used.

Example 64 Preparation of hydroxypropyl-heptaisooctyloctasilsesquioxanefrom a Compound (136)

A compound represented by formula (150) can be prepared as in example 45except that in place of compound (131), the compound (136) prepared inexample 36 or 43 is used.

Example 65 Preparation ofhydroxypropyl-heptatrifluoropropyloctasilsesquioxane from a Compound(137)

A compound represented by formula (151) can be prepared as in example 54except that in place of compound (131), the compound (137) prepared inexample 37 or 44 is used.

Example 66 Preparation of a Compound of Sodium-Boundtridecafluoro-1,1,2,2-tetrahydrooctylsilsesquioxane fromtridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane

Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (4.9 g),tetrahydrofuran (15 mL), sodium hydroxide (0.2 g), and ion-exchangewater (0.2 g) were placed into a 50-mL four-necked flask equipped with astirring bar, a reflux condenser, a thermometer and a dropping funnel.The reactants were stirred at the reflux temperature of 75° C. Afterfive hours of reflux with stirring, the reaction was completed. Theresulting solution was condensed by heating under reduced pressure. Thecondensate was dried with a vacuum dryer at 80° C. for three hours toobtain a glutinous liquid (4.0 g).

Example 67 Introduction of Trimethylsilyl Groups

The above powdery solid (2.6 g), tetrahydrofuran (10 g), triethylamine(1.0 g) and trimethylchlorosilane (3.3 g) were placed into a 50-mL threenecked flask, and stirred with a magnetic stirrer at room temperaturefor three hours. After the reaction was completed, treatment procedureswere applied as in example 16 to obtain a glutinous liquid (1.3 g).

Analysis by gel permeation chromatography showed that the resultingproduct was monodispersed, possessed a weight-average molecular weightrelative to polystyrene standards of 3650 (uncorrected) and had a purityof 100%. These results, 5 combined with those of examples 3 to 16,suggest the resulting liquid was the silicon compound of formula (152).This suggests that the compound prepared in example 66 exhibited thestructure represented by formula (153).

Example 68 Preparation of a Compound of Silanol-Containingtridecafluoro-1,1,2,2-trahydrooctylsilsesquioxane from a Compound (153)

A compound represented by formula (154) can be prepared as in example 30except that the starting material is a compound (153), and in place ofbutyl acetate, AK225 is used as the reaction solvent.

Example 69 Preparation ofacetoxyethyl-heptatridecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxanefrom a Compound (153)

A compound represented by formula (155) can be prepared as in example 2310 except that the starting material is a compound (153), and in placeof tetrahydrofuran, AK225 is used as the reaction solvent.

Example 70 Preparation ofacetoxypropyl-heptatridecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxanefrom a Compound (153)

A compound represented by formula (156) can be prepared as in example 31except that the starting material is a compound (153), and in place oftetrahydrofuran, AK225 is used as the reaction solvent.

Example 71 Preparation ofacetoxyethyl-heptatridecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxanefrom a Compound (154)

A compound (155) can be prepared by reacting a compound (154) withacetoxyethyltrichlorosilane in the presence of triethylamine as inexamples 24 to 30 except that the starting material is a compound (154)and the reaction solvent is AK225.

Example 72 Preparation ofacetoxypropyl-heptatridecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxanefrom a Compound (154)

A compound (156) can be prepared by reacting acetoxyethyltrichlorosilanein the presence of triethylamine as in examples 38 to 44 except that thestarting material is a compound (154) and the reaction solvent is AK225.

Example 73 Preparation ofhydroxyethyl-heptatridecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxanefrom a Compound (155)

A compound represented by formula (157) can be prepared as in examples54 to 58 except that the starting material is the compound (155)prepared in example 69 or 71.

Example 74 Preparation ofhydroxypropyl-heptatridecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxanefrom a Compound (156)

A compound represented by formula (158) can be prepared as in examples54 to 58 except that the starting material is the compound (156)prepared in example 70 or 72.

1. A silicon compound represented by formula (1), being prepared from asilicon compound represented by formula (2),

wherein: in formula (1), each of seven R¹ is independently selected fromthe group consisting of (a) hydrogen, (b) (ii) 2-methylpropyl, (iii)2,4,4-trimethylpentyl, (iv) cyclopentyl, (v) cyclohexyl, (vi)trifluoropropyl, (vii) tridecafluoro-1,1,2,2,-tetrahydrooctyl and (viii)unsubstituted phenyl, (c) substituted or unsubstituted aryl and (d)substituted or unsubstituted arylalkyl wherein each hydrogen of thealkenylene may be optionally substituted with fluorine and each —CH₂—group of said alkenylene may be optionally replaced with —O— or —CH═CH—;and A² is a hydroxyl-terminal organic group, and in formula (2), R¹ isthe same as R¹ in formula (1) and A¹ is an organic compound having anacyloxy group.
 2. The silicon compound according to claim 1, wherein (a)in formula (1), all of seven R¹ are the same functional groups selectedfrom the group consisting of (ii) 2-methylpropyl, (iii)2,4,4-trimethylpentyl, (iv) cyclopentyl, (v) cyclohexyl, (vi)trifluoropropyl, (vii) tridecafluoro-1,1,2,2,-tetrahydrooctyl and (viii)unsubstituted phenyl; (b) A² is a group represented by formula (3) and(c) A¹ in formula (2) is a group represented by formula (4),

wherein: in formula (3), Z¹ is either C₁-C₂₂ alkylene where each —CH₂—group may be optionally replaced with —O—, or C₃-C₈ alkenylene whereeach —CH₂— group may be optionally replaced with —O—; in formula (4), R²is selected from the group consisting of C₁-C₁₇ alkyl where eachhydrogen may be optionally substituted with fluorine, C₂-C₃ alkenyl,substituted or unsubstituted phenyl and unsubstituted phenylalkyl, andZ¹ is the same as Z¹ in formula (3).
 3. The silicon compound accordingto claim 1, wherein (a) in formula (1), all of seven R¹ are the samefunctional groups selected from the group consisting of (ii)2-methylpropyl, (iii) 2,4,4-trimethylpentyl, (iv) cyclopentyl, (v)cyclohexyl, (vi) trifluoropropyl, (vii)tridecafluoro-1,1,2,2,-tetrahydrooctyl and (viii) unsubstituted phenyl;(b) A² is a group represented by formula (5) and (c) A¹ in formula (2)is a group represented by formula (6),

wherein: in formula (5), (A) Z² represents a single bond or C₁-C₃alkylene and may be bound to the benzene ring at any carbon position,(B) Z³ is either C₁-C₂₂ alkylene where each —CH₂— may be optionallyreplaced with —O—, or C₃-C₈ alkenylene where each —CH₂— may beoptionally replaced with —O—, in formula (6), R² is selected from thegroup consisting of C₁-C₁₇ alkyl, C₂-C₃ alkenyl, substituted orunsubstituted phenyl and unsubstituted phenylalkyl, and Z² and Z³ arethe same as Z² and Z³ in formula (5).
 4. The silicon compound accordingto claim 2, wherein all of seven R¹ are either unsubstituted phenyl ortrifluoropropyl.
 5. The silicon compound according to claim 3, whereinall of seven R¹ are either unsubstituted phenyl or trifluoropropyl.
 6. Asilicon compound represented by formula (1),

wherein: in formula (1), each of seven R¹ is independently selected fromthe group consisting of (a) hydrogen, (b) (ii) 2-methylpropyl, (iii)2,4,4-trimethylpentyl, (iv) cyclopentyl,(v) cyclohexyl, (vi)trifluoropropyl, (vii) tridecafluoro-1,1,2,2,-tetrahydrooctyl and (viii)unsubstituted phenyl, (c) substituted or unsubstituted aryl and (d)substituted or unsubstituted arylalkyl wherein each hydrogen of thealkenylene may be optionally substituted with fluorine and each —CH₂—group of said alkenylene may be optionally replaced with —O— or —CH═CH—;and A² is a hydroxyl-terminal organic group.
 7. The silicon compoundaccording to claim 6, wherein (a) in formula (1), all of seven R¹ arethe same functional groups selected from the group consisting of (ii)2-methylpropyl, (iii) 2,4,4-trimethylpentyl, (iv) cyclopentyl, (v)cyclohexyl, (vi) trifluoropropyl, (vii)tridecafluoro-1,1,2,2,-tetrahydrooctyl and (viii) unsubstituted phenyl;and (b) A₂ is a group represented by formula (3),

wherein: in formula (3), Z¹ is either C₁-C₂₂ alkylene where each —CH₂—group may be optionally replaced with —O—, or C₃-C₈ alkenylene whereeach —CH₂— group may be optionally replaced with —O—.
 8. The siliconcompound according to claim 6, wherein (a) in formula (1), all of sevenare the same functional groups selected from the group consisting of(ii) 2-methylpropyl, (iii) 2,4,4-trimethylpentyl, (iv) cyclopentyl, (v)cyclohexyl, (vi) trifluoropropyl, (vii)tridecafluoro-1,1,2,2,-tetrahydrooctyl and (viii) unsubstituted phenyl;and (b) A² is a group represented by formula (5),

wherein: in formula (5), (A) Z² represents a single bond or C₁-C₃alkylene and may be bound to the benzene ring at any carbon position,and (B) Z³ is either C₁-C₂₂ alkylene where each —CH₂— may be optionallyreplaced with —O—, or C₃-C₈ alkenylene where each —CH₂— may beoptionally replaced with —O—.
 9. The silicon compound according to claim7, wherein all, of seven R¹ are either unsubstituted phenyl ortrifluoropropyl.
 10. The silicon compound according to claim 8, whereinall of seven R¹ are either unsubstituted phenyl or trifluoropropyl.